Exhaust gas purification catalyst and production method thereof

Abstract

This catalyst includes a lower catalytic layer 2 having catalytic ability to oxidize HC and CO and an upper catalytic layer 3 having catalytic ability to reduce NO.sub.x. The lower catalytic layer 2 contains Pt and Pd acting as catalytic metals, zeolite, a Ce-containing oxide, and activated alumina, and the upper catalytic layer 3 contains activated alumina loading an Rh-doped Ce-containing oxide and an NO.sub.x storage material.

Claims

1. An exhaust gas purification catalyst comprising: a lower catalytic layer having catalytic ability to oxidize HC and CO on a substrate; and an upper catalytic layer having catalytic ability to reduce NO.sub.x on top of, or above, the lower catalytic layer, wherein the lower catalytic layer contains Pt and Pd acting as catalytic metals, zeolite, Ce-containing oxide, and activated alumina, the upper catalytic layer contains activated alumina loading an Rh-doped Ce-containing oxide and an alkali earth metal acting as an NO.sub.x storage material, the lower catalytic layer includes a first oxidation catalyst layer containing activated alumina loading Pt and Pd and a Ce-containing oxide loading Pt and Pd, and a second oxidation catalyst layer containing zeolite loading Pt and Pd, and the second oxidation catalyst layer is disposed on the first oxidation catalyst layer.

2. The exhaust gas purification catalyst of claim 1, wherein an intermediate catalytic layer is provided between the lower and upper catalytic layers, the intermediate catalytic layer containing Pt and Rh acting as catalytic metals, activated alumina, a Ce-containing oxide and an NOx storage material, and containing no Pd.

3. The exhaust gas purification catalyst of claim 1, wherein the substrate has a hexagonal cell honeycomb structure with a hexagonal cell cross section.

4. A method for producing an exhaust gas purification catalyst, the method comprising: forming, on a substrate, a lower catalytic layer including Pt and Pd acting as catalytic metals, zeolite, a Ce-containing oxide, and activated alumina; and forming, on the lower catalytic layer, an upper catalytic layer including activated alumina loading an Rh-doped Ce-containing oxide and an alkali earth metal acting as an NO.sub.x storage material, wherein in the forming the upper catalytic layer, a mixture of a coprecipitated hydroxide containing Ce and Rh, and activated alumina is calcined to prepare the activated alumina loading the Rh-doped Ce-containing oxide, the activated alumina loading the Rh-doped Ce-containing oxide is applied directly or indirectly onto the lower catalytic layer, the applied layer is impregnated with the NO.sub.x storage material, and is calcined, and in the forming the lower catalytic layer, a first oxidation catalyst layer containing activated alumina loading Pt and Pd and a Ce-containing oxide loading Pt and Pd is formed on the substrate, and a second oxidation catalyst layer containing zeolite loading Pt and Pd is formed on the first oxidation catalyst layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a cross-sectional view illustrating a portion of an exhaust gas purification catalyst.

(2) FIG. 2 is a cross-sectional view illustrating how respective catalytic layers are stacked one upon the other in an exhaust gas purification catalyst according to a first embodiment.

(3) FIG. 3 is a schematic representation of alumina loading an Rh-doped Ce-containing oxide.

(4) FIG. 4 is a cross-sectional view illustrating how respective catalytic layers are stacked one upon the other in an exhaust gas purification catalyst according to a second embodiment.

(5) FIG. 5 is a cross-sectional view illustrating how respective catalytic layers are stacked one upon the other in an exhaust gas purification catalyst according to a third embodiment.

(6) FIG. 6 is a flowchart showing respective process steps to be performed to produce an exhaust gas purification catalyst.

(7) FIG. 7 is a graph showing how the total HC concentration of a gas emitted from the catalyst and a catalyst entrance temperature change during an HC purification performance evaluation test.

(8) FIG. 8 is a graph showing HC purification rates in examples and a comparative example.

(9) FIG. 9 is a graph showing how the NO.sub.x concentration of a gas emitted from the catalyst changes during an NO.sub.x purification performance evaluation test.

(10) FIG. 10 is a graph showing NO.sub.x purification rates in the examples and the comparative example.

DESCRIPTION OF EMBODIMENTS

(11) Embodiments of the present invention will now be described with reference to the drawings. Note that the following description of preferred embodiments is merely illustrative in nature, and is not intended to limit the scope, applications, and use of the present disclosure.

(12) An exhaust gas purification catalyst described herein is suitable for purifying an exhaust gas of a diesel engine of an automobile, and disposed in an exhaust passage of the diesel engine. A DPF is disposed in the exhaust passage downstream of the exhaust gas purification catalyst.

(13) FIG. 1 illustrates a basic configuration for the exhaust gas purification catalyst. In FIG. 1, the reference character 1 denotes the cell wall of a honeycomb substrate. A lower catalytic layer 2 is formed on the cell wall 1, and an upper catalytic layer 3 is formed on the lower catalytic layer 2. The space surrounded with the upper catalytic layer 3 serves as an exhaust gas passage 4. The honeycomb substrate has a hexagonal cell honeycomb structure with a hexagonal cell cross section. In FIG. 1, the catalytic layers 2 and 3 are illustrated as being provided for only one cell for the sake of simplicity. However, the catalytic layers 2 and 3 are actually provided for every cell.

(14) As illustrated in FIG. 2, according to a first preferred embodiment, the lower catalytic layer 2 contains, as DOC components, zeolite loading Pt and Pd, activated alumina loading Pt and Pd, and an oxygen storage capacity (OSC) material loading Pt and Pd. The OSC material is made of a Ce-containing oxide. The lower catalytic layer 2 is implemented as a DOC layer. The upper catalytic layer 3 contains alumina loading an Rh-doped Ce-containing oxide (hereinafter referred to as Rh-doped Ce-containing oxide-loading alumina) as an LNT catalytic component. Furthermore, Pt and Rh acting as LNT catalytic metals and an NO.sub.x storage material are loaded into the LNT catalytic component of the upper catalytic layer 3 by some impregnation method. The upper catalytic layer 3 is implemented as an LNT catalytic layer. Pt, Rh, and the NO.sub.x storage material (alkali earth metal) are partially loaded into the DOC components of the lower catalytic layer 2.

(15) The Rh-doped Ce-containing oxide-loading alumina is a catalytic component loading an Rh-doped Ce-containing oxide 12 on activated alumina 11 as illustrated in FIG. 3, and Rh 13 is loaded on the activated alumina 11 through the Ce-containing oxide.

(16) As illustrated in FIG. 4, according to a second preferred embodiment, although the upper catalytic layer 3 has the same configuration as its counterpart of the first embodiment, the lower catalytic layer 2 is comprised of a first oxidation catalyst layer 2a and a second oxidation catalyst layer 2b stacked on the first oxidation catalyst layer 2a. The first oxidation catalyst layer 2a contains, as DOC components, activated alumina loading Pt and Pd and an OSC material loading Pt and Pd. The second oxidation catalyst layer 2b contains zeolite loading Pt and Pd as a DOC component. The DOC components of the oxidation catalyst layers 2a and 2b are loaded with small amounts of Pt, Rh, and the NO.sub.x storage material.

(17) As illustrated in FIG. 5, according to a third preferred embodiment, although the lower catalytic layer 2 (comprised of the first and second oxidation catalyst layers 2a and 2b) and the upper catalytic layer 3 have the same configuration as their counterparts of the second embodiment, an intermediate catalytic layer 5 is interposed between the lower and upper catalytic layers 2 and 3. The intermediate catalytic layer 5 includes activated alumina and an OSC material, which are partially loaded with LNT catalytic metals (Pt, Rh) and NO.sub.x storage material introduced by the impregnation method mentioned above.

(18) The intermediate catalytic layer 5 can also be provided between the lower catalytic layer 2 and the upper catalytic layer 3 when the lower catalytic layer 2 is formed by a single layer like the first embodiment.

(19) (Method for Producing Exhaust Gas Purification Catalyst)

(20) FIG. 6 shows respective manufacturing process steps to be performed to produce an exhaust gas purification catalyst.

(21) [Formation of Lower Catalytic Layer 2]

(22) A lower catalytic layer 2 is formed on a honeycomb substrate by applying slurry including a DOC powder and a binder to the honeycomb substrate, drying and then calcining the slurry. If the lower catalytic layer 2 has a double-layer structure comprised of the first and second oxidation catalyst layers 2a and 2b as in the second and third embodiments, slurry for the first oxidation catalyst layer is applied, dried, and calcined, and then, slurry for the second oxidation catalyst layer is applied, dried, and calcined.

(23) Preparation of DOC Powder

(24) If the lower catalytic layer 2 is a single layer as in the first embodiment, zeolite, activated alumina, and an OSC material are mixed together, and catalytic metals (Pt and Pd) to make a DOC are loaded on the mixture by evaporation to dryness method. Specifically, water is added to the mixture and the resulting mixture is stirred to prepare slurry mixture. While this slurry mixture is being stirred, a nitrate solution in which the catalytic metals are dissolved is dropped onto the slurry mixture. Then, the resulting slurry mixture is further stirred while being heated to vaporize the water completely. The resulting dried mixture is calcined in the air and then pulverized. As a result, a DOC powder is obtained (as a mixture of zeolite, activated alumina, and the OSC material each loading the catalytic metals to make the DOC).

(25) If the lower catalytic layer 2 has a double-layer structure comprised of the first and second oxidation catalyst layers 2a and 2b as in the second and third embodiments, the catalytic metals to make the DOC are partially loaded on the mixture of the activated alumina and the OSC material by the evaporation to dryness method to obtain a DOC powder for the first oxidation catalyst layer. The rest of the catalytic metals to make the DOC is loaded on zeolite by the evaporation to dryness method to obtain a DOC powder for the second oxidation catalyst layer.

(26) Preparation of Slurry

(27) A slurry is obtained by mixing the DOC powder with a binder and water, adding a nitric acid aqueous solution for adjusting the viscosity of the slurry to the mixture, and stirring the resulting mixture.

(28) [Formation of Intermediate Catalytic Layer 5]

(29) If an intermediate catalytic layer 5 is formed as in the third embodiment, an applied layer to be the intermediate catalytic layer is formed by mixing activated alumina, an OSC material, a binder, and water together to prepare a slurry, applying the slurry onto the lower catalytic layer 2 on the honeycomb substrate, and drying and then calcining the slurry.

(30) [Formation of Upper Catalytic Layer 3]

(31) An applied layer to be the upper catalytic layer is formed by applying slurry containing a binder and an LNT catalytic powder (activated alumina loading an Rh-doped Ce-containing oxide) onto the lower catalytic layer 2 of the honeycomb substrate (or onto the intermediate catalytic layer 5 in the third embodiment), drying and then calcining the slurry.

(32) Preparation of LNT Catalytic Powder

(33) Cerium nitrate and rhodium nitrate are dissolved in deionized water and stirred. While this nitrate solution (acid solution) is stirred, ammonia water is added to the nitrate solution to allow neutralization of the nitrate solution. As a result, Ce and Rh are coprecipitated as a hydroxide (which produces a precursor of an Rh-doped Ce-containing oxide). In the neutralization, another alkaline solution such as caustic soda solution may be used instead of the ammonia water.

(34) Activated alumina is added to the solution containing the coprecipitated hydroxide, and the resulting solution is stirred sufficiently. This solution is processed by a centrifuge to remove the supernatant liquid. Next, deionized water is further added to the solution, and the resulting solution is stirred and processed by the centrifuge, again. This dehydration and washing processes are repeated a required number of times. Such dehydration and washing processes remove the redundant basic solution. The gelatinous block thus obtained is dried, and then calcined and pulverized. In this manner, activated alumina loading an Rh-doped Ce-containing oxide is obtained.

(35) If the Rh-doped Ce-containing oxide is obtained by coprecipitating Ce and Rh as described above, Ce oxide (ceria) is doped with Rh. In the step of preparing the nitrate solution, addition of a nitrate of any other transition metal such as Zr, Pr, or Nd can also produce an Rh-doped Ce-based composite oxide.

(36) [Impregnation of LNT Catalytic Metal and NO.sub.x Storage Material]

(37) The honeycomb substrate including the applied layer to be the upper catalytic layer is impregnated with a mixed solution of LNT catalytic metals (Pt and Rh) and an NO.sub.x storage material. This mixed solution is mainly introduced into the applied layer to be the upper catalytic layer, and is also partially introduced into the applied layer to be the intermediate catalytic layer or the lower catalytic layer 2.

(38) [Drying and Calcination]

(39) The honeycomb substrate in which the applied layer has been impregnated with the mixed solution is dried and calcined. As a result, formed is an upper catalytic layer 3 into which the LNT catalytic metals (Pt and Rh) and the NO.sub.x storage material are loaded as a result of the impregnation. In the third embodiment, formed is an intermediate catalytic layer 5 into which the LNT catalytic metals (Pt and Rh) and the NO.sub.x storage material are loaded as a result of the impregnation.

(40) In the method for producing an exhaust gas purification catalyst described above, the substrate may be dried by maintaining the substrate in the air at a temperature of about 100 C.-250 C. for a predetermined time, for example. The substrate may be calcined by maintaining the substrate in the air at a temperature of about 400 C.-600 C. for a few hours, for example.

(41) (Evaluation of HC Purification Performance and NO.sub.x Purification Performance)

(42) Honeycomb catalysts were prepared as Examples 1-3 and Comparative Example by the method of producing an exhaust gas purification catalyst described above, and HC purification performance and NO.sub.x purification performance were evaluated. In each of Examples 1-3 and Comparative Example, a cordierite hexagonal-cell honeycomb substrate (with a diameter of 24.5 mm and a length of 50 mm) having a cell wall thickness of 4.5 mil (1.14310.sup.1 mm) and including 400 cells per square inch (645.16 mm.sup.2) was used as a substrate. A CePr composite oxide (with a mass ratio of CeO.sub.2:Pr.sub.6O.sub.11=90:10) was used as an OSC material. -zeolite was used as zeolite. The calcination during the catalytic powder preparation, the calcination after the application of the catalytic powder, and the calcination of the LNT catalytic metals and the NO.sub.x storage material after the impregnation were all performed in the air at a temperature of 500 C. for two hours.

EXAMPLE 1

(43) Example 1 is a honeycomb catalyst such as the one illustrated in FIG. 2 according to the first embodiment. The amounts of the respective loaded catalytic components (i.e., amount per 1 L of the substrate, as will be applied to the rest of the description) in the lower catalytic layer (single layer) 2 are zeolite=100 g/L, activated alumina=60 g/L, OSC material=40 g/L, Pt=1.6 g/L, and Pd=0.8 g/L. The LNT catalytic powder of the upper catalytic layer 3 is an Rh-doped Ce oxide-loading alumina containing 0.4 g/L of Rh, 2 g/L of CeO.sub.2, and 18 g/L of activated alumina. The LNT catalytic metals introduced by the impregnation method are Pt and Rh, and the NO.sub.x storage materials are Ba and Sr. The amounts of the respective loaded components are Pt=4.3 g/L, Rh=0.1 g/L, Ba=30 g/L, and Sr=10 g/L.

EXAMPLE 2

(44) Example 2 is a honeycomb catalyst such as the one illustrated in FIG. 4 according to the second embodiment. The amounts of the respective loaded catalytic components in the first oxidation catalyst layer 2a are activated alumina=60 g/L, OSC material=40 g/L, Pt =1.2 g/L, and Pd=0.6 g/L. The amounts of the respective loaded catalytic components in the second oxidation catalyst layer 2b are zeolite=100 g/L, Pt=0.4 g/L, and Pd=0.2 g/L. The upper catalytic layer 3 is made up of the same components as its counterpart of Example 1. The amounts of respective Pt and Rh introduced as LNT catalytic metals by the impregnation method, and the amounts of respective Ba and Sr introduced as NO.sub.x storage materials by the impregnation method are the same as those of Example 1.

EXAMPLE 3

(45) Example 3 is a honeycomb catalyst such as the one illustrated in FIG. 5 according to the third embodiment. The amounts of the respective loaded catalytic components in the intermediate catalytic layer are activated alumina=40 g/L, and OSC material=40 g/L. The first oxidation catalyst layer 2a, the second oxidation catalyst layer 2b, and the upper catalytic layer 3 have the same components as their counterparts of Example 2. The amounts of respective Pt and Rh introduced as LNT catalytic metals by the impregnation method, and the amounts of respective Ba and Sr introduced as NO.sub.x storage materials by the impregnation method are the same as those of Example 1.

COMPARATIVE EXAMPLE

(46) The comparative example is a honeycomb catalyst having the same configuration as Example 1, except that an Rh-loading alumina is adopted as the LNT catalytic powder of the upper catalytic layer. The Rh-loading alumina is obtained by loading Rh on activated alumina by the evaporation to dryness method, and contains 0.4 g/L of Rh, and 18 g/L of activated alumina.

(47) Measurement of HC Purification Rate

(48) The respective honeycomb catalysts of Example 1-3 and Comparative Example were subjected to an aging treatment in a gas atmosphere comprising 2% of O.sub.2, 10% of H.sub.2O, and N.sub.2 as the balance at 800 C. for 24 hours. The honeycomb catalysts were loaded into a model gas flow reactor, and the gas temperature at a catalyst entrance was maintained at 100 C. with N.sub.2 gas allowed to circulate through the honeycomb catalysts. Then, a model gas for evaluating the HC purification performance was introduced.

(49) The model gas has a composition including 600 ppmC of n-octane, 150 ppmC of ethylene, 50 ppmC of propylene, 1500 ppm of CO, 30 ppm of NO, 10% of O.sub.2, 10% of H.sub.2O, and N.sub.2 as the balance, and its space velocity was 72000/h.

(50) The gas temperature at the catalyst entrance started to be increased when two minutes passed since the model gas had started to be introduced, and a total HC concentration (THC) of the gas emitted from the honeycomb catalyst was measured. FIG. 7 shows an exemplary result of the measurement.

(51) The temperature of the catalyst is low for a while after the model gas has started to be introduced, and therefore, HC in the model gas gets adsorbed on zeolite. Therefore, the THC of the emitted gas is lower than 800 ppmC that is the THC of the model gas. The amount of HC adsorbed on zeolite gradually decreases as the catalyst temperature rises. And when the gas temperature at the catalyst entrance reaches the vicinity of 200 C., the amount of HC desorbed exceeds the amount of HC adsorbed on zeolite, and the THC begins to rise steeply to be higher than 800 ppmC. The higher the catalyst temperature, the more and more active the catalyst gets to allow DOC to start purifying the desorbed HC. As a result, the THC falls steeply to be lower than 800 ppmC.

(52) Then, the HC purification rate of each of the honeycomb catalysts of Examples 1-3 and Comparative Example was calculated for a period between a point in time when the model gas started to be introduced and a point in time when the gas temperature reached 300 C. Here, the HC purification rate was calculated by subtracting the amount of HC desorbed (C) from the sum of the decrease in THC (A) caused by the HC adsorption and the decrease in THC (B) caused by the HC purification as shown in FIG. 7. The results are shown in FIG. 8.

(53) Measurement of NO.sub.x Purification Rate

(54) The respective honeycomb catalysts of Examples 1-3 and Comparative Example were subjected to the same aging treatment as when the HC purification rate was measured, and then loaded into a model gas flow reactor. The gas temperature at a catalyst entrance was maintained at 200 C. with model gas with a rich air-fuel ratio allowed to circulate through the honeycomb catalyst. The gases were changed into a model gas with a lean air-fuel ratio with that temperature maintained, and the gases were changed once again into a model gas with a rich air-fuel ratio when 180 seconds passed since the model gases were changed.

(55) FIG. 9 shows an exemplary result of measurement of an NO.sub.x concentration of the gas emitted from the honeycomb catalyst. The NO.sub.x concentration starts to increase as soon as the types of the model gas are changed from rich to lean, and continues to rise with time after that. Then, as the NO.sub.x storage amount gets close to a saturation point, the NO.sub.x concentration of the model gas approaches 220 ppm asymptotically. When the type of the model gas is changed from lean to rich, NO.sub.x is released from the NO.sub.x storage material. However, since a reducing agent (HC and CO) is supplied due to the change into the rich type, NO.sub.x gets reduced by Pt and Rh at a steep rate. As a result, the NO.sub.x concentration of the emitted gas decreases steeply.

(56) The NO.sub.x purification rate for 190 seconds in total was calculated based on the decrease in NO.sub.x (A) caused by NO.sub.x storage for 180 seconds in a lean state and the decrease in NO.sub.x (B) caused by NO.sub.x reduction for 10 seconds in a rich state as shown in FIG. 9. The average NO.sub.x purification rate for 190 seconds in total was calculated in the same way with the gas temperature at the catalyst entrance set to be 250 C.

(57) The rich model gas has a composition including 220 ppm of NO, 3400 ppmC of HC, 1.0% of CO, 0.5% of O.sub.2, 6% of CO.sub.2, 10% of H.sub.2O, and N.sub.2 as the balance. The lean model gas has a composition including 220 ppm of NO, 400 ppmC of HC, 0.15% of CO, 10% of O.sub.2, 6% of CO.sub.2, 10% of H.sub.2O, and N.sub.2 as the balance. The results are shown in FIG. 10.

(58) Results of Measurement of HC Purification Ratio and NO.sub.x Purification Rate

(59) According to FIGS. 8 and 10, the HC purification rate and the NO.sub.x purification rate in Example 1 are larger than in the Comparative Example. This shows that use of an Rh-doped Ce-containing oxide-loading alumina as an LNT catalyst for the upper catalytic layer effectively improves purification performance of HC and NO.sub.x.

(60) That is probably because an Rh-doped Ce-containing oxide-loading alumina in Example 1 causes a smaller degree of degradation since the aging (at 800 C. for 24 hours) reduces burial of Rh in alumina, compared to the Rh-loading alumina of the Comparative Example. In addition, the increase in the NO.sub.x reduction activity of Rh caused by the Ce-containing oxide would also have led to the excellent result of Example 1.

(61) Look at the results obtained in Examples 1-3, and it can be seen that Example 2 having a triple-layer structure has a higher HC purification rate and a higher NO.sub.x purification rate than Example 1 having a double-layer structure. This shows that it is preferable to dispose the lower catalytic layer 2 having a double-layer structure such that activated alumina and the OSC material are contained in the first oxidation catalyst layer 2a as the lower layer, and zeolite is contained in the second oxidation catalyst layer 2b as the upper layer. Example 3 having a quadruple-layer structure has an even higher HC purification rate and an even higher NO.sub.c purification rate than Example 2 having a triple-layer structure. This is probably because the multilayered structure reduces the amount of the LNT catalytic metal and the NO.sub.x storage material introduced into the lower catalytic layer 2.

DESCRIPTION OF REFERENCE CHARACTERS

(62) 1 substrate (cell wall)

(63) 2 lower catalytic layer

(64) 2a first oxidation catalyst layer

(65) 2b second oxidation catalyst layer

(66) 3 upper catalytic layer

(67) 5 intermediate catalytic layer

(68) 11 activated alumina

(69) 12 Rh-doped Ce-containing oxide

(70) 13 Rh