Patent Publication Number: US-6217831-B1

Title: Catalyst for purifying exhaust gases

Description:
This is a Continuation of application Ser. No. 08/625,922 filed Apr. 1, 1996 now U.S. Pat. No. 5,849,254, which in turn is a Continuation Application of application Ser. No. 08/366,506 filed Dec. 30, 1994, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a catalyst for purifying exhaust gases from automobiles, and more particularly, to a catalyst which can efficiently purify nitrogen oxides (NO x ) in exhaust gases in oxygen-rich atmospheres whose oxygen concentrations are more than required for oxidizing carbon monoxide (CO) and hydrocarbons (HC) therein. 
     2. Description of the Related Art 
     As catalysts for purifying automotive exhaust gases, there have been employed 3-way catalysts so far which oxidize CO and HC and reduce NO x  simultaneously into innocuous entities. For example, 3-way catalysts have been known widely which comprise a heat resistant support formed of cordierite, a catalyst carrier layer formed of gamma-alumina and disposed on the support, and a noble metal catalyst selected from the group consisting of Pt, Pd, and Rh and loaded on the catalyst carrier layer. 
     The purifying performance of these 3-way catalysts for purifying exhaust gases largely depends on the air-fuel ratio (A/F) of automotive engines. For instance, when the air-fuel ratio is large, i.e., when the fuel concentration is small (or on the fuel-lean side), the oxygen concentration is large in exhaust gases. Accordingly, the reactions of oxidizing CO and HC are active, but the reactions of reducing NO x  are inactive. On the other hand, when the air-fuel ratio is small, i.e., when the fuel concentration is high (or on the fuel-rich side), the oxygen concentration is small in exhaust gases. Accordingly, the oxidation reactions are inactive, but the reduction reactions are active. 
     Moreover, when driving automobiles, especially when driving automobiles in urban areas, the automobiles are accelerated and decelerated frequently. Accordingly, the air-fuel ratio varies frequently in a range from the values adjacent to the stoichiometric point (or the ideal air-fuel ratio) to the fuel-rich side. In order to satisfy the low fuel consumption requirement during the driving in urban areas, it is necessary to operate automobiles on the fuel-lean side where the air-fuel mixture containing as excessive oxygen as possible is supplied to the engines. Hence, it has been desired to develop a catalyst which is capable of adequately purifying NO x  on the fuel-lean side (i.e., in the oxygen-rich atmospheres). 
     In view of the aforementioned circumstances, the applicants of the present invention applied for a Japanese Patent for a novel catalyst under Japanese Unexamined Patent Publication (KOKAI) No.5-317,652. This catalyst comprises a support, and an alkaline-earth metal and Pt loaded on the support. With this support, NO x  are adsorbed on the alkaline-earth metal when the air-fuel ratios are on the fuel-lean side (i.e., in the oxygen-rich atmospheres) driving. Then, when the automobiles are driven under the air-fuel ratios at the stoichiometric point or on the fuel-rich side (i.e., in the oxygen-lean atmospheres), NO x  are purified by reacting with reducing gases such as HC and the like. Thus, this catalyst is superb in the NO x  purifying performance even on the fuel-lean side (i.e., in the oxygen-rich atmospheres). 
     This catalyst is believed to adsorb NO x  by the following mechanism: The alkaline-earth metal, for example, Ba is loaded on the support in a form of the simple oxide. The simple oxide of Ba reacts with NO x  to produce barium nitrate (Ba(NO 3 ) 2 ). Thus, NO x  are adsorbed on the support of the catalyst. 
     However, the exhaust gases usually contain SO 2  which is produced by burning sulfur (S) contained in the fuel. The catalyst ingredient further oxidizes SO 2  to SO 3  in the oxygen-rich atmospheres (i.e., on the fuel-lean side). Then it has become apparent that SO 3  reacts readily with water also contained in the exhaust gases to produce sulfuric acid, and that the resulting sulfuric acid reacts with Ba to produce sulfite and/or sulfate, which do not adsorb NO x . When Ba or the like is converted into sulfite or sulfate, it cannot adsorb NO x  any more. As a result, this catalyst suffers from a drawback in that it is deteriorated in terms of the NO x  purifying performance after it has been used for a long time. 
     SUMMARY OF THE INVENTION 
     The present invention has been developed in view of the aforementioned circumstances. It is therefore an object of the present invention to provide a catalyst which can efficiently purify nitrogen oxides (NO x ) in exhaust gases in oxygen-rich atmospheres whose oxygen concentrations are more than required for oxidizing CO and HC. It is an another object of the present invention to provide a catalyst which attains improved NO x  purifying performance after it has been used for a long time by preventing an NO x  absorber from degraded due to its generation of salts of SO x . 
     A catalyst for purifying exhaust gases according to a first aspect of the present invention comprises, being arranged in an order from the upstream to the downstream of exhaust gas flow, a first catalyst in which a noble metal catalyst is loaded on a porous acidic support, a second catalyst in which at least one kind of NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals, and rare earth metals is loaded on a porous support, and a third catalyst in which a noble metal catalyst is loaded on a porous support. 
     A catalyst for purifying exhaust gases according to a second aspect of the present invention is a catalyst in which at least one kind of NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals and rare earth metals, and a noble metal catalyst are loaded on a porous support, and the surface layer of the porous support includes oxides of at least one metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and manganese (Mn). 
     In the catalyst for purifying exhaust gases according to the first aspect of the present invention, first, automotive exhaust gases contact the first catalyst. This first catalyst has a property of not adsorbing SO 2 , because the support is acidic. Therefore, SO 2  is prevented from being adsorbed on the support and from being oxidized by the noble metal catalyst, and most SO 2  flows into the second catalyst as it is. When a metal such as nickel (Ni), iron (Fe), zinc (Zn), and vanadium (V) is loaded in addition to the noble metal catalyst, SO 2  is more securely prevented from oxidation. This is supposed to be because these metals serve to decrease the oxidation force of the noble metal catalyst. 
     The porous acidic support of the first catalyst is suitably formed from materials such as SiO 2 , ZrO 2 , SiO 2 —Al 2 O 3 , TiO 2 , and so on. 
     The exhaust gases flowing into the second catalyst contain almost no SO 3  for the reason described in the above. Therefore, at least one kind of NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals, and rare earth metals is prevented from generating salts with SO 3 , and can adsorb NO x  in the exhaust gases efficiently. It has been apparent that NO 2  is better adsorbed by NO x  absorbers than NO. NO in the exhaust gases in oxygen-rich atmospheres is efficiently oxidized by the first catalyst and flows into the second catalyst in the form of NO 2  and other NO x . Therefore, the NO x  absorber in the second catalyst efficiently adsorbs NO x . In this way, the exhaust amounts of NO x  in the fuel-lean atmosphere are decreased. 
     Then, the NO x  adsorbed by the second catalyst is discharged when the air-fuel ratio is at the stoichiometric point or on the fuel-rich side, and flows into the third catalyst where the NO x  is reduced into innocuous entity by 3-way activity. 
     Examples of the suitable porous supports of the second catalyst and the third catalyst include Al 2 O 3 , zeolite, SiO 2 , ZrO 2 , and SiO 2 —Al 2 O 3 . Al 2 O 3  is most preferable. The supports can be formed from these porous bodies in themselves, or formed by coating honeycombs made of cordierite, heat-resistant metals or the like with these porous bodies. 
     In the second catalyst, it is also preferable to load a transition metal in addition to at least one kind of NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals, and rare earth metals. This transition metal may be loaded by adding not only as a simple substance but also as a composite oxide such as BaCuO 2 , LaCoO 3 , LaBaCoO 3 . The loading of this transition metal allows the temperature window of NO x  purifying performance to be transferred in the direction of higher temperatures. 
     For example, when Ba alone is loaded, the peak temperature of NO x  purifying performance is 250° C., but when Ba and Cu are loaded, the peak temperature moves to 400° C., and when Ba and Co are loaded, the peak temperature moves to 450° C., and when Ba and Fe are loaded, the peak temperature moves to 400° C. Further, the loading of plural kinds of metals achieves an increase in the width of the temperature window. This offers an advantage of providing greater freedom in installing catalysts. It must be noted that transition metals exhibit lower oxidization catalyst performance than noble metal catalysts. Therefore, almost no SO 3  generates in the second catalyst, and at least one kind of NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals, and rare earth metals is able to exhibit the function of adsorbing NO x  to the maximum. 
     In the catalyst for purifying exhaust gases according to the second aspect of the present invention, the surface layer of the porous support includes oxides of at least one metal selected from the group consisting of Fe, Co, Ni, Cu and Mn. These metal oxides have the function of oxidizing SO 2  into SO 3  although this function is not strong, and the metal oxides take in SO 3  and H 2 SO 4  which is formed by reacting SO 3  with water, and form salts of SO x . Therefore, SO x  do not reach the NO x  absorber which exists inside of the support and accordingly the NO x  absorber is prevented from generating salts of SO x . 
     The above metal oxides generate salts of SO x  and NO x , respectively, but the salts of NO x  decompose at about 300° C. and the salts of SO x  decompose at about 500° C. Therefore, at the time of ordinary driving where the inlet automotive exhaust gas temperature to the bed of catalyst is approximately in a range from 300 to 400° C., the NO x  which were taken in and formed into salts decompose soon and are taken in by the NO x  absorber on the inside of the porous support. Further, the metal oxides which once decomposed and regenerated adsorb SO x  and form salts of SO x . On the other hand, at the time of ordinary driving, SO x  exist in the form of salts, and accordingly, do not react with the NO x  absorber. Therefore, the NO x  absorber is prevented from being degraded due to its generation of salts of SO x , and the salts of metal oxide and SO x  decompose approximately above 500° C. and SO x  are discharged downstream. 
     It is necessary that SO 2  and NO are oxidized into SO 3  and NO 2  respectively in order to react with the metal oxides and generate salts. In the second aspect of the invention, a noble metal catalyst, when loaded on the surface layer in addition to the metal oxides, promotes the oxidation of NO and the resulting NO 2  reacts with the metal oxides and generates salts. Accordingly, NO is prevented from being discharged downstream. In the meanwhile, the noble metal catalyst also promotes the oxidation of SO 2 , and the taking in of the resulting SO x  by the above metal oxides is given preference over other elements. As described in the above, NO 2  is quickly taken in by the NO x  absorber and the taken-in NO x  securely react with HC or CO when the fuel-air ratio is at the stoichiometric point. As a result, the NO x  purifying performance even after used for a long time is improved. 
     The catalyst for purifying exhaust gases according to the present invention has the following advantages. 
     According to the present invention, at least one kind of loaded NO x  absorber selected from the group consisting of alkali metals, alkaline-earth metals, and rare earth metals is prevented from contacting SO 3 . Therefore, the NO x  absorber is free from degradation caused by its generation of sulfite and/or sulfate. Therefore, the catalyst exhibits high NO x  purifying performance even after it has been used for a long time and is superior in durability. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     A more complete appreciation of the present invention and many of its advantages will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings and detailed specification, all of which forms a part of the disclosure: 
     FIG. 1 is a perspective view of a catalyst for purifying exhaust gases according to a first preferred embodiment of the present invention; 
     FIG. 2 is a cross-sectional view for explaining the constitution of the catalyst for purifying exhaust gases according to the first preferred embodiment of the present invention; and 
     FIG. 3 is a cross-sectional view for explaining the constitution of a catalyst for purifying exhaust gases according to a fifth preferred embodiment of the present invention. 
    
    
     THE PREFERRED EMBODIMENTS OF THE PRESENT INVENTION 
     Having generally described the present invention, a further understanding can be obtained by reference to the specific preferred embodiments which are provided herein for purposes of illustration only and are not intended to limit the scope of the appended claims. 
     The First Preferred Embodiment 
     FIG.  1  and FIG. 2 show a catalyst for purifying exhaust gases according to a first preferred embodiment of the present invention. This catalyst comprises a first catalyst  1 , a second catalyst  2 , and a third catalyst  3 , being arranged axially. The respective catalysts have the same diameters and the axial length of the first catalyst, the second catalyst and the third catalyst has a ratio of 2:6:2. This catalyst is used by arranging the first catalyst  1  in the upper stream of the exhaust gases. 
     The first catalyst  1  comprises a first honeycomb support  10  formed of cordierite, a first catalyst carrier layer  11  formed of SiO 2  and coated on the surface of the first honeycomb support  10 , and platinum (Pt)  12  loaded on the first carrier layer  11 . 
     The second catalyst  2  comprises a second honeycomb support  20  formed of cordierite, a second catalyst carrier layer  21  formed of Al 2 O 3  and coated on the surface of the second honeycomb support  20 , and barium (Ba)  22  loaded on the second carrier layer  21 . 
     The third catalyst  3  comprises a third honeycomb support  30  formed of cordierite, a third catalyst carrier layer  31  formed of Al 2 O 3  and coated on the surface of the third honeycomb support  30 , and platinum (Pt)  32  and Rh (rhodium)  33  loaded on the third catalyst layer  31 . 
     Now, we will describe a method of producing this catalyst instead of describing its constitution in detail. It must be noted that hereinafter, parts mean parts by weight. 
     &lt;The First Catalyst&gt; 
     100 parts of porous silica powder, 70 parts of silica sol containing silica in an amount of 10% by weight, and 30 parts of water were stirred, thereby preparing slurry for coating. 
     Next, the first honeycomb support  10  formed of cordierite was immersed in water and blown to blow away excessive water. Then the first support  10  was immersed in this slurry and blown to blow away an excess of the slurry, dried at 80° C. for 20 minutes, and calcined at 600° C. for one hour, thereby forming the first carrier layer  11  on the support  10 . The SiO 2  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support  10 . 
     The honeycomb support thus coated with SiO 2  was immersed into an aqueous bivalent platinum ammine hydroxide solution. After pulled up and blown to blown away water droplets in excess, it was calcined at 250° C. for one hour. The loading amount of platinum (Pt) was 2.0 grams with respect to 1 liter of the honeycomb support  10 . 
     &lt;The Second Catalyst&gt; 
     100 parts of alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of a 40% by weight solution of aluminum nitrate in water, and 30 parts of water were mixed, thereby preparing slurry for coating. 
     This slurry was coated on the second honeycomb support  20  in the same way as in the first catalyst, thereby forming the second catalyst carrier layer  21 . The Al 2 O 3  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support  20 . 
     The honeycomb support coated with Al 2 O 3  was immersed in an aqueous barium acetate solution. After pulled up and blown to blow away water droplets in excess, it was dried at 110° C. for 12 hours and calcined at 600° C. for one hour. The loading amount of barium (Ba)  22  was 0.3 mol with respect to 1 liter of the honeycomb support  20 . 
     &lt;The Third Catalyst&gt; 
     100 parts of alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of a 40% by weight solution of aluminum nitrate in water, and 30 parts of water were mixed, thereby preparing slurry for coating. 
     This slurry was coated on the third honeycomb support  30  in the same way as in the first catalyst, thereby forming the third carrier layer  31 . The Al 2 O 3  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support  30 . 
     The honeycomb support coated with Al 2 O 3  was immersed in an aqueous platinum dinitrodiammine solution. After pulled up and blown to blow away water droplets in excess, it was calcined at 250° C. for one hour. Next, it was immersed in an aqueous rhodium nitrate solution. After pulled up and blown to blow away water droplets in excess, it was calcined at 250° C. for one hour. The loading amount of platinum (Pt)  32  was 2.0 grams with respect to 1 liter of the honeycomb support  30 , and the loading amount of rhodium (Rh)  33  was 2.0 grams with respect to 1 liter of the honeycomb support  30 . 
     The first catalyst  1 , the second catalyst  2  and the third catalyst  3  thus produced were axially arranged in this order without providing space therebetween. Thus, the catalyst according to the first preferred embodiment of the present invention was produced. 
     The Second Preferred Embodiment 
     &lt;The First Catalyst&gt; 
     100 parts of porous silica powder, 70 parts of silica sol containing silica in an amount of 10% by weight, and  30  parts of water were stirred, thereby preparing slurry for coating. 
     Next, a honeycomb support formed of cordierite was immersed in water, and after blown to blow away excessive water, it was immersed in this slurry. After pulled up and blown to blow away the slurry in excess, it was dried at 80° C. for 20 minutes and calcined at 600° C. for one hour. The SiO 2  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support. 
     The honeycomb support thus coated with SiO 2  was immersed in an aqueous bivalent platinum ammine hydroxide solution. After pulled up and blown to blow away water droplets in excess, it was calcined at 250° C. for one hour. The loading amount of Pt was 2.0 grams with respect to 1 liter of the honeycomb support. The production method described so far was the same as the method of producing the first catalyst of the first preferred embodiment. 
     Next, the amount of water to be absorbed by the obtained honeycomb support was measured, and an aqueous nickel acetate solution was prepared to have concentration at which that amount of water absorption contained nickel by 3% by weight based on the honeycomb support. Then the honeycomb support was immersed in this solution. After pulled up and blown to blow away water droplets in excess, it was dried at 110° C. for 12 hours and calcined at 600° C. for one hour, thereby loading nickel and forming the first catalyst of the second preferred embodiment of the present invention. 
     &lt;The Second Catalyst&gt; 
     100 parts of alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of a 40% by weight solution of aluminum nitrate in water, and 30 parts of water were commingled, thereby preparing slurry for coating. 
     This slurry was coated on the honeycomb support in the same way as in the first preferred embodiment. The Al 2 O 3  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support. 
     This honeycomb support coated with Al 2 O 3  was immersed in an aqueous copper acetate solution. After pulled up and blown to blow away water droplets in excess, it was dried at 110° C. for 12 hours and calcined at 600° C. for three hours, thereby loading copper (Cu). The loading amount of Cu was 8% by weight based on the alumina coating. 
     The obtained honeycomb support was further immersed in an aqueous barium acetate solution. After pulled up and blown to blow away water droplets in excess, it was dried at 110° C. for 12 hours and calcined at 600° C. for one hour. The loading amount of Ba was 0.3 mol with respect to 1 liter of the honeycomb support. 
     &lt;The Third Catalyst&gt; 
     This was produced in the same way as the third catalyst of the first preferred embodiment. 
     The Third Preferred Embodiment 
     &lt;The First Catalyst&gt; 
     This was produced in the same way as the first catalyst of the second preferred embodiment, except that slurry for coating was prepared by mixing 100 parts of zirconia powder, 70 parts of zirconia sol containing zirconia in an amount of 10% by weight, and 30 parts of water. 
     &lt;The Second Catalyst&gt; 
     This was produced in the same way as the second catalyst of the second preferred embodiment. 
     &lt;The Third Catalyst&gt; 
     This was produced in the same way as the third catalyst of the second preferred embodiment. 
     The Fourth Preferred Embodiment 
     &lt;The First Catalyst&gt; 
     This was produced in the same way as the first catalyst of the second preferred embodiment. 
     &lt;The Second Catalyst&gt; 
     This was produced in the same way as the second catalyst of the second preferred embodiment, except that slurry for coating was prepared by mixing 60 parts of alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of a 40% by weight solution of aluminum nitrate in water, 30 parts of water, and 100 parts of YBa 2 Cu 3 O 7  powder. The Al 2 O 3  coating was in an amount of 60 grams with respect to 1 liter of the honeycomb support. 
     &lt;The Third Catalyst&gt; 
     This was produced in the same way as the third catalyst of the second preferred embodiment. 
     The First Comparative Example 
     100 parts of alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of a 40% by weight solution of aluminum nitrate in water, and 30 parts of water were mixed, thereby preparing slurry for coating. 
     A honeycomb support formed of cordierite was immersed in this slurry. After blown to blow away the slurry in excess and dried, it was calcined at 600° C. for one hour, thereby forming an alumina coating layer. The Al 2 O 3  coating was in an amount of 120 grams with respect to 1 liter of the honeycomb support. 
     The honeycomb support having this alumina coating layer was immersed in an aqueous platinum dinitrodiammine solution. After blown to blow away water droplets in excess, it was dried at 250° C., thereby loading platinum (Pt). The loading amount of Pt was 2.0 grams with respect to 1 liter of the honeycomb support. 
     Next, this Pt-loaded honeycomb support was immersed in an aqueous barium acetate solution having a predetermined concentration. After blown to blow away water droplets in excess and dried, it was calcined at 600° C. for one hour, thereby preparing a comparative catalyst. The loading amount of Ba was 0.3 mol with respect to 1 liter of the support. 
     Examination and Evaluation 
     Each of the present catalysts and the comparative catalyst was disposed in an exhaust line of an actual vehicle equipped with a lean burn engine which had a displacement of 1.6 liters. The vehicle was driven in the urban area running modes, i.e., the 10-mode and the 15-mode, thereby examining the present catalysts and the comparative catalyst for the conversion of CO, HC, and NO x . 
     After the aforementioned evaluation, each of the present catalysts and the comparative catalyst was subjected to a bench test on durability which utilized the same type of engine as above. That is to say, each of them was disposed in an exhaust line of the engine, and then the engine was run for 50 hours while adjusting the inlet exhaust gas temperature to the bed of catalyst at 650° C. and keeping the ratio of air to fuel at 18. After this bench test was over, each of them was again disposed in the exhaust line of the actual vehicle. The vehicle was driven in the same manner as described above, thereby examining the present catalysts and the comparative catalyst for the conversion of CO, HC, and NO x  after the durability test. The fuel employed included sulfur in an amount of 70 ppm. The test results are shown in Table 1. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                   
                   
                 Initial 
                 Conversion After 
               
               
                   
                 Coating 
                 Loaded 
                 Conversion (%) 
                 Durability Test (%) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Catalyst 
                 Layer 
                 Metal 
                 NO x   
                 HC 
                 CO 
                 NO x   
                 HC 
                 CO 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Example 1 
                 1st 
                 SiO 2   
                 Pt 
                 40 
                 93 
                 100 
                 36 
                 89 
                 92 
               
               
                   
                 2nd 
                 Al 2 O 3   
                 Ba 
               
               
                   
                 3rd 
                 Al 2 O 3   
                 Pt, Rh 
               
               
                 Example 2 
                 1st 
                 SiO 2   
                 Pt, Ni 
                 65 
                 95 
                 100 
                 57 
                 89 
                 94 
               
               
                   
                 2nd 
                 Al 2 O 3   
                 Ba, Cu 
               
               
                   
                 3rd 
                 Al 2 O 3   
                 Pt, Rh 
               
               
                 Example 3 
                 1st 
                 ZrO 2   
                 Pt, Ni 
                 66 
                 96 
                 100 
                 58 
                 90 
                 98 
               
               
                   
                 2nd 
                 Al 2 O 3   
                 Ba, Cu 
               
               
                   
                 3rd 
                 Al 2 O 3   
                 Pt, Rh 
               
               
                 Example 4 
                 1st 
                 SiO 2   
                 Pt, Ni 
                 62 
                 92 
                  99 
                 55 
                 86 
                 93 
               
               
                   
                 2nd 
                 Al 2 O 3   
                 YBa 2 Cu 3 O 7   
               
               
                   
                 3rd 
                 Al 2 O 3   
                 Pt, Rh 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Comparative 
                 Al 2 O 3   
                 Pt, Ba 
                 93 
                 95 
                 100 
                 50 
                 88 
                 98 
               
               
                 Example 1 
               
               
                   
               
            
           
         
       
     
     It is appreciated from Table 1 that although the initial NO x  conversion performance of the present catalysts was not as good as that of the comparative catalyst, the ratios of the NO x  conversion performance after the durability test to the initial NO x  conversion performance (the NO xc  conversion performance after the durability test/the initial NO x  conversion performance) of the present catalysts were superior to that of the comparative catalyst by far. That is to say, the present catalysts had NO x  conversion performance less deteriorated by the durability test, and were superior in durability to the comparative catalyst. 
     The Fifth Preferred Embodiment 
     FIG. 3 shows an enlarged cross-sectional view of a part of catalyst for purifying exhaust gases according to a fifth preferred embodiment of the present invention. This catalyst comprises a honeycomb support  4 , an inner catalyst carrier layer  5  formed on the surface of the honeycomb support  4 , an outer catalyst carrier layer  6  formed on the surface of the inner carrier layer  5 . Platinum (Pt)  50  and barium (Ba)  51  are loaded on the inner carrier layer  5 , and Fe 2 O 3    60  is loaded on the outer carrier layer  6 . 
     This catalyst for purifying exhaust gases was produced as follows. First, 150 g of water and 350 g of alumina sol containing alumina in an amount of 10% by weight were added to 500 g of alumina powder and stirred, thereby preparing slurry A. In the meanwhile, 175 g of alumina sol containing alumina in an amount of 10% by weight was added to 250 g of alumina powder and 125 g of Fe 2 O 3  powder, and stirred, thereby preparing slurry B. 
     Next, a honeycomb support formed of cordierite was immersed in slurry A. After pulled up and blown to blow away the slurry in excess, it was dried at 80° C. for twenty minutes and calcined at 500° C. for one hour, thereby forming the inner carrier layer  5  by 100 g per liter. Then it was immersed in an aqueous platinum dinitrodiammine solution. After pulled up and blown to blow away water droplets in excess, it was dried at 80° C. and calcined at 500° C. Further it was immersed in an aqueous barium acetate solution, and pulled up and blown to blow away water droplets in excess. Then it was dried at 80° C. and calcined at 500° C. Thus, Pt and Ba were loaded on the inner carrier layer  5 . 
     After that, the support  4  having the above inner carrier layer  5  thereon was immersed in slurry B. After pulled up and blown to blow away the slurry in excess, it was dried at 80° C. for twenty minutes and calcined at 500° C. for one hour, thereby forming the outer carrier layer  6  by 50 g per liter. 
     As shown in Table 2, the catalyst thus obtained had Pt in an amount of 1.0 g/liter and Ba in an amount of 0.2 mol/liter on the inner carrier layer  5 , and Fe in an amount of 0.2 mol/liter on the outer carrier layer  6 . 
     The Sixth Preferred Embodiment 
     This was produced in the same way as the catalyst of the fifth preferred embodiment, except that La was loaded instead of Ba, and MnO 2  was loaded instead of Fe 2 O 3 . 
     The Seventh Preferred Embodiment 
     This was produced in the same way as the catalyst of the fifth preferred embodiment, except that the outer carrier layer  6  was formed from slurry comprising 100 g of iron oxide powder and 100 g of alumina sol containing alumina in an amount of 10% by weight. In other words, the outer carrier layer  6  mainly comprised iron oxide and included alumina only by about 10% by weight. 
     The Eighth and Ninth Preferred Embodiments 
     These were produced in the same way as the catalyst of the seventh preferred embodiment, except that the kinds and amounts of loading metals are those shown in Table 2. 
     The Tenth Preferred Embodiment 
     250 g of alumina powder and 125 g of Fe 2 O 3  powder were added to an aqueous platinum dinitrodiammine solution and stirred, thereby loading Pt on the powder. After filtered, it was dried and calcined, thereby obtaining Pt-loaded powder. 150 g of water and 350 g of alumina sol containing alumina in an amount of 10% by weight were added to 375 g of this Pt-loaded powder, and stirred, thereby obtaining slurry B. The outer carrier layer  6  was made from slurry B by 50 g/liter. A catalyst of the tenth preferred embodiment was produced in the same way as that of the fifth preferred embodiment, except the aforementioned facts. That is to say, in this catalyst, Pt in addition to Fe was loaded on the outer carrier layer  6  by 0.3 g/liter. 
     The Eleventh to Eighteenth Preferred Embodiments 
     These were produced in the same way as the catalyst of the tenth preferred embodiment, except that the kinds and amounts of loading metals were those shown in Table 2. 
     The Second to Fourth Comparative Examples 
     These were produced in the same way as the first comparative catalyst, except that the kinds and amounts of loading metals were those shown in Table 2. 
     Examination and Evaluation 
     Each of the present catalysts and the comparative catalysts was disposed in an exhaust line of an actual vehicle equipped with a lean burn engine which had a displacement of 1.6 liters. The vehicle was driven in the urban area running modes, i.e., the 10-mode and the 15-mode, thereby examining the present catalysts and the comparative catalysts for the conversion of CO, HC and NO x . 
     After the aforementioned evaluation, each of the present catalysts and the comparative catalysts was subjected to a bench test on durability which utilized the same type of engine as above. That is to say, each of them was disposed in an exhaust line of the engine, and then the engine was run for 50 hours while adjusting the inlet exhaust gas temperature to the bed of catalyst at 650° C. and keeping the ratio of air to fuel at 18. After this bench test was over, each of them was again disposed in the exhaust line of the actual vehicle. The vehicle was driven in the same manner as described above, thereby examining the present catalysts and the comparative catalysts for the conversion of CO, HC, and NO x  after the durability test. The fuel employed included sulfur in an amount of 70 ppm. The test results are shown in Table 2. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Inner Carrier 
                 Load Amount of 
                 Outer Carrier 
                 Load Amount of 
                 Initial 
                 Conversion after 
               
               
                   
                 Layer 
                 Element (g, mol/L) 
                 Layer 
                 Element (g, mol/L) 
                 conversion (%) 
                 Durability Test (%) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Pt 
                 Pd 
                 Ba 
                 La 
                 Li 
                 K 
                 Na 
                 Pt 
                 Pb 
                 Mn 
                 Fe 
                 Co 
                 Ni 
                 Cu 
                 NO x   
                 HC 
                 CO 
                 NO x   
                 HC 
                 CO 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Examples 
                  5 
                 1.0 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 92 
                 96 
                  98 
                 70 
                 96 
                 99 
               
               
                   
                  6 
                 1.0 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 87 
                 98 
                 100 
                 69 
                 95 
                 99 
               
               
                   
                  7 
                 1.0 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 93 
                 96 
                 100 
                 60 
                 94 
                 97 
               
               
                   
                  8 
                 1.0 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 90 
                 99 
                 100 
                 58 
                 97 
                 98 
               
               
                   
                  9 
                 1.0 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 88 
                 96 
                 100 
                 57 
                 94 
                 98 
               
               
                   
                 10 
                 1.0 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 88 
                 96 
                 100 
                 68 
                 96 
                 99 
               
               
                   
                 11 
                 1.0 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 84 
                 98 
                 100 
                 65 
                 95 
                 98 
               
               
                   
                 12 
                 1.0 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 81 
                 97 
                 100 
                 68 
                 96 
                 98 
               
               
                   
                 13 
                 1.0 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 0.5 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 86 
                 96 
                  98 
                 64 
                 96 
                 98 
               
               
                   
                 14 
                 1.0 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.2 
                 0.5 
                 — 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 92 
                 96 
                  99 
                 67 
                 94 
                 99 
               
               
                   
                 15 
                 — 
                 2.0 
                 0.3 
                 — 
                 0.1 
                 — 
                 — 
                 — 
                 0.5 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 89 
                 97 
                  98 
                 71 
                 94 
                 99 
               
               
                   
                 16 
                 — 
                 2.0 
                 — 
                 0.3 
                 — 
                 0.1 
                 — 
                 — 
                 0.5 
                 — 
                 — 
                 0.3 
                 — 
                 — 
                 87 
                 96 
                  99 
                 65 
                 94 
                 99 
               
               
                   
                 17 
                 — 
                 2.0 
                 — 
                 — 
                 0.1 
                 — 
                 0.3 
                 — 
                 1.0 
                 — 
                 — 
                 — 
                 0.3 
                 — 
                 90 
                 97 
                  99 
                 70 
                 95 
                 99 
               
               
                   
                 18 
                 — 
                 2.0 
                 0.2 
                 — 
                 — 
                 — 
                 0.2 
                 — 
                 1.0 
                 — 
                 — 
                 — 
                 — 
                 0.3 
                 91 
                 95 
                  98 
                 71 
                 93 
                 99 
               
               
                 Comparative 
                  2 
                 1.0 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 91 
                 96 
                 100 
                 48 
                 92 
                 96 
               
               
                 Examples 
                  3 
                 — 
                 2.0 
                 0.3 
                 — 
                 0.1 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 93 
                 96 
                 100 
                 45 
                 93 
                 98 
               
               
                   
                  4 
                 1.0 
                 — 
                 — 
                 0.2 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 88 
                 98 
                 100 
                 46 
                 96 
                 99 
               
               
                   
               
            
           
         
       
     
     It is appreciated from Table 2 that although the initial NO x  conversion performance of the present catalysts was not as good as that of the comparative examples, the ratios of the NO x  conversion performance after the durability test to the initial NO x  conversion performance (the NO x  conversion performance after the durability test/the initial NO x  conversion performance) of the present catalysts were superior to those of the comparative catalysts by far. That is to say, the present catalysts had NO x  conversion performance less deteriorated by the durability test, and were superior in durability to the comparative catalysts. 
     Having now fully described the present invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the present invention as set forth herein including the appended claims.