Patent Publication Number: US-2010111827-A1

Title: PRODUCTION PROCESS FOR NOx ADSORPTION MATERIAL AND NOx ADSORPTION MATERIAL

Description:
TECHNICAL FIELD 
     The present invention relates to an NO x  adsorption material that is used for converting the exhaust gases of automobile, and to a production process for the same. 
     BACKGROUND ART 
     As a catalyst for converting exhaust gas, catalyst which is for lean-burn engine, an NO x  storage-and-reduction type catalyst has been used, NO x  storage-and-reduction type catalyst which includes a noble metal and an NO x  storage material. This NO x  storage-and-reduction type catalyst stores NO x  into the NO x  storage material in lean atmosphere, and converts NO x , which have been released from the NO x  storage material at the time of rich spiking, by reduction by means of reducing components, such as HC, which exist abundantly in the atmosphere. 
     However, in the NO x  storage-and-reduction type catalyst, it is difficult to store NO x  in low-temperature region like at the time of starting up, and so forth, and accordingly there has been such a drawback that NO x  have been discharged in the low-temperature region. Hence, it has been thought of using an NO x  adsorption material that is capable adsorbing NO x  in the low-temperature region, and an exhaust-gas converting apparatus, in which an NO x  adsorption material is put in place on the upstream side of an NO x  storage-and-reduction type catalyst, is proposed in Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2001-289,035, for instance. 
     As for the NO x  adsorption material, the oxides of alkali metals, the oxides of alkaline-earth metals, transition-metal oxides, such as CO 3 O 4 , NiO 2 , MnO 2 , Fe 2 O 3  and ZrO 2 , and zeolite are exemplified in the aforementioned gazette. Moreover, in Japanese Unexamined Patent Publication (KOKAI) Gazette No. 7-163,871, an NO x  adsorption material is disclosed, NO x  adsorption material which comprises CeO 2  and zeolite; and, in Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2005-514,551, an NO x  adsorption material is disclosed, NO x  adsorption material which comprises zeolite that is ion exchanged with a base metal, such as Fe, Cu and Mn. 
     Patent Literature No. 1: Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2001-289,035; 
     Patent Literature No. 2: Japanese Unexamined Patent Publication (KOKAI) Gazette No. 7-163,871; and 
     Patent Literature No. 3: Japanese Unexamined Patent Publication (KOKAI) Gazette No. 2005-514,551 
     DISCLOSURE OF THE INVENTION 
     Assignment to be Solved by the Invention 
     As a result of studying various NO x  adsorption materials, the inventors of the present application found out that an NO x  adsorption material, which is completed by ion exchanging zeolite with Fe, exhibits high NO x  adsorbing capacity in low-temperature region. And, according to a liquid-phase exchanging method that uses an aqueous solution of water-soluble Fe salt, although the amount of ion exchanged Fe is less so that it is difficult to demonstrate desirable characteristics, it became apparent that a great amount of Fe can be ion exchanged by using a gas-phase exchanging method, which utilizes the sublimation of ferric chloride, and thereby an NO x  adsorption material that is good in terms of NO x  adsorbing characteristic is obtainable. 
     According to the gas-phase exchanging method utilizing the sublimation of ferric chloride, a zeolite powder is impregnated with an FeCl 3  aqueous solution, and thereafter FeCl 3  is vaporized by heating it to 330° C. or more, the sublimation temperature of FeCl 3  or more. The vaporized FeCl 3  goes into the pores of zeolite, and is then supported on the cation exchange sites by means of ion exchange. 
     However, as a result of studying NO x  adsorption materials that were produced by the vapor-phase exchanging method in more detail, it became apparent that the resulting NO x  adsorbing performance lowers greatly after a hydrothermal durability test. 
     The present invention is one which has been done in view of the aforementioned circumstances, and it is an assignment to be solved to make it into an NO x  adsorption material that has high NO x  adsorbing performance even after a hydrothermal durability test. 
     Means for Solving the Assignment 
     A characteristic of a production process according to the present invention lies in that: 
     an impregnating step of impregnating a zeolite having cation exchange sites with a ferric chloride aqueous solution, thereby turning it into a ferric chloride-containing zeolite; and 
     an ion exchanging step of heating the ferric chloride-containing zeolite at 500° C.-700° C. in an atmosphere that is free from moisture, thereby subjecting Fe to ion exchange; are carried out in this order. 
     Effect of the Invention 
     In accordance with the production process for NO x  adsorption material according to the present invention, it is surely possible to stably produce an NO x  adsorption material that demonstrates high NO x  adsorbing performance even after a hydrothermal durability test, and that is good in terms of durability. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a graph for illustrating the NO adsorption amounts of NO x  adsorption materials according to examples and comparative examples at their initial stages; 
         FIG. 2  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 300° C.; 
         FIG. 3  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 400° C.; 
         FIG. 4  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 500° C.; 
         FIG. 5  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 600° C.; 
         FIG. 6  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 700° C.; 
         FIG. 7  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 800° C.; 
         FIG. 8  is a graph for illustrating the NO adsorption amounts of the NO x  adsorption materials according to the examples and comparative examples after undergoing a hydrothermal durability test at 900° C.; and 
         FIG. 9  is a graph for illustrating the NO adsorption amounts of NO x  adsorption materials according to reference examples at their initial stages, and those after undergoing a hydrothermal durability test at 400° C. 
     
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     As for a zeolite having cation exchange sites, although ZSM-5, mordenite, β-zeolite, type Y zeolite, type L zeolite, and the like, have been known, it become apparent that, in the zeolites other than mordenite, the hydrothermal durability of NO x  adsorption materials, which are obtained by subjecting Fe to ion exchange by means of the aforementioned process, is not sufficient. 
     Hence, it is an assignment of a production process for NO x  adsorption material according to the present invention, even when the zeolites other than mordenite are used, to adapt them into NO x  adsorption materials that are good in terms of durability. In the present invention, it is possible to use ZSM-5, type Y zeolite and type L zeolite as the zeolite, and it is naturally possible to use mordenite, too. 
     In the production process according to the present invention, a ferric chloride-containing zeolite is prepared first of all by impregnating a zeolite having cation exchange sites with an FeCl 3  aqueous solution. It is feasible to subject Fe to ion exchange to a certain extent even by a method in which an FeCl 3  powder is sublimed after mixing the FeCl 3  powder with a zeolite powder physically. However, since the ion-exchange rate is low so that FeCl 3  escaping to the outside becomes greater, a method of impregnating it with an aqueous solution has been employed. 
     As for an impregnation amount of FeCl 3 , it is desirable to impregnate a zeolite with it in an amount of the same mole as that of the Al atoms in the zeolite or more. This is because of the fact that, in a zeolite, ion exchange sites exist in an amount of the same number as the number of Al atoms, and accordingly the resulting NO x  adsorbing performance improves the most in the case where all of them are ion exchanged with Fe. 
     Therefore, since it is preferable to use those with a great amount of cation exchange sites for a zeolite, it is desirable to use those whose SiO 2 /Al 2 O 3  molar ratio is 200 or less therefor. Moreover, although it is possible to use type H and type NH 4  zeolites, it is preferable to use a type NH 4  that is good in terms of ion exchanging property in the case of utilizing a vapor-phase exchanging method that uses FeCl 3 . 
     At the ion exchanging step, the ferric chloride-containing zeolite is heated at 500° C.-700° C. in an atmosphere that is free from moisture, and thereby Fe is subjected to ion exchange. Even when using a zeolite such as ZSM-5, it is possible to produce an NO x  adsorption material, which demonstrates high NO x  adsorbing performance even after a hydrothermal durability test, by thus heating the ferric chloride-containing zeolite at high temperatures in an atmosphere that is free from moisture. When the heating temperature in the ion exchanging step is less than 500° C., the hydrothermal durability of the NO x  adsorbing performance in the obtained NO x  adsorption materials declines. Moreover, even when heating it beyond 700° C., the hydrothermal durability of the NO x  adsorbing performance declines, though the reason has been unclear. 
     It is adapted herein into an atmosphere that is free from moisture, because the resulting NO x  adsorbing performance declines when it is heated in an atmosphere that contains moisture; and it is believed to result from the fact that the degradation by means of aluminum elimination has been facilitated. 
     Examples 
     Hereinafter, the present invention will be explained in detail by means of examples and comparative examples. 
     Example No. 1 
     NH 4 -ZSM-5 whose SiO 2 /Al 2 O 3  molar ratio was 28 was made ready, and was then impregnated within an FeCl 3  aqueous solution in such a charging amount that the Fe atoms made 1:1 with respect to the Al atoms. After evaporating this to dryness by heating it at 120° C., it was then heated to 500° C. by an electric furnace in an atmosphere that was free from moisture, and was held thereat for 5 hours. By means of this, FeCl 3  sublimed to vaporize, and thereby almost all of the cation exchange sites of the ZSM-5 were ion exchanged with Fe. 
     Example No. 2 
     The same zeolite as that of Example No. 1 was used; was ion exchanged with Fe similarly; and thereafter the ion exchanging step was carried out in the same manner as Example No. 1, except that the heating temperature was adapted into being 600° C. 
     Example No. 3 
     The same zeolite as that of Example No. 1 was used; was ion exchanged with Fe similarly; and thereafter the ion exchanging step was carried out in the same manner as Example No. 1, except that the heating temperature was adapted into being 700° C. 
     Comparative Example No. 1 
     The same zeolite as that of Example No. 1 was used; was ion exchanged with Fe similarly; and thereafter the ion exchanging step was carried out in the same manner as Example No. 1, except that the heating temperature was adapted into being 400° C. 
     Comparative Example No. 2 
     The same zeolite as that of Example No. 1 was used; was ion exchanged with Fe similarly; and thereafter the ion exchanging step was carried out in the same manner as Example No. 1, except that the heating temperature was adapted into being 800° C. 
     Comparative Example No. 3 
     The same zeolite as that of Example No. 1 was used; was ion exchanged with Fe similarly; and thereafter the ion exchanging step was carried out in the same manner as Example No. 1, except that the heating temperature was adapted into being 900° C. 
     Testing Example No. 1 
     The NO x  adsorption materials according to the respective examples and respective comparative examples were pelletized by an ordinary method, respectively, and were then offered for testing. Each of the pellets was charged into an evaluating apparatus in a predetermined amount; first of all, a model gas given in Table 1 was distributed at a temperature of 50° C. in a flow volume of 10 L/min. for 8 minutes; and the adsorption amounts of NO (initial NO adsorption amounts) that had been adsorbed during the period were measured, respectively. The results are illustrated in  FIG. 1 . 
     Next, regarding the respective NO x  adsorption materials, a hydrothermal durability test was carried out, hydrothermal durability test in which they were held at 300° C., 400° C., 500° C., 600° C., 700° C., 800° C. and 900° C., respectively, for 5 hours in atmospheres in which an N 2  gas, which included 10% H 2 O and 2% CO, and another N 2  gas, which included 2% O 2 , were flowed while switching them alternately for 5 minutes each. 
     After doing purging by distributing a 500-° C. N 2  gas with respect to the respective NO x  adsorption materials after the hydrothermal durability test, the model gas given in Table 1 was distributed at a temperature of 50° C. in a flow volume of 10 L/min. for 8 minutes, and the adsorption amounts of NO that had been adsorbed during the period were measured, respectively. The results are illustrated in  FIG. 2  through  FIG. 8 . 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 NO 
                 CO 
                 CO 2   
                   
               
               
                 (ppm) 
                 (ppm) 
                 (%) 
                 N 2   
               
               
                   
               
             
            
               
                 900 
                 6000 
                 15 
                 Balance 
               
               
                   
               
            
           
         
       
     
     From  FIG. 2-FIG .  8 , in accordance with the NO x  adsorption materials according to Example Nos. 1-3 that were subjected to the ion-exchange processing at 500° C.-700° C., it is apparent that their high NO x  adsorbing performance was maintained even after the hydrothermal durability test at 300° C.-700° C. 
     Moreover, from  FIG. 1 , it is understood that the lower the heating temperature at the time of ion exchanging the higher the initial NO adsorption amount was, and that, considering the initial NO x  adsorbing performance alone, the heating at 400° C. like Comparative Example No. 1 can be the most preferable. However, in Comparative Example No. 1, the NO adsorption amount was declined less than the initial value by carrying out the hydrothermal durability test at 500° C.-700° C.; whereas, in the NO x  adsorption material according to Example No. 1, it was equivalent to the initial value substantially; and, in the NO x  adsorption materials according to Example Nos. 2-3, their NO adsorption amounts were augmented contrarily. 
     Specifically, taking the durability of NO x  adsorbing performance at the time of service into consideration, it is apparent that it is desirable to do the ion-exchange processing at 500° C.-700° C. 
     Reference Example No. 1 
     NH 4 -ZSM-5 whose SiO 2 /Al 2 O 3  molar ratio was 28 was made ready in an amount of 20 g, and was then impregnated within an aqueous solution in which anhydrous FeCl 3  was dissolved in an amount of 3.4 g. After evaporating this to dryness by heating it at 120° C., it was then heated to 400° C. by an electric furnace in an atmosphere that was free from moisture, and was held thereat for 5 hours. By means of this, FeCl 3  sublimed to vaporize, and thereby almost all of the cation exchange sites of the ZSM-5 were ion exchanged with Fe. 
     Reference Example No. 2 
     Instead of the ZSM-5, an H-mordenite powder whose SiO 2 /Al 2 O 3  molar ratio was 28 was made ready, and Fe was subjected to ion exchange in the same manner as Reference Example No. 1. 
     Testing Example No. 2 
     The NO x  adsorption materials according to Reference Example Nos. 1 and 2 were pelletized by an ordinary method, respectively, and were then offered for testing. Each of the pellets was charged into an evaluating apparatus in a predetermined amount; first of all, the adsorption amounts of NO were measured in the same manner as Testing Example No. 1. Subsequently, the same hydrothermal durability test as that in Testing Example No. 1 was carried out, thereby measuring the NO adsorption amounts after the hydrothermal durability test. The results are illustrated in  FIG. 9 . 
     From  FIG. 9 , although the NO x  adsorption material according to Reference Example No. 1 using the ZSM-5 exhibited an NO adsorption amount, which was equivalent to that of the NO x  adsorption material according to Reference Example No. 2 using the mordenite, at the initial stage, the NO adsorption amount declined greatly after the hydrothermal durability test. Specifically, it is apparent that the NO x  adsorption material according to Reference Example No. 1 using the ZSM-5 was poor in terms of durability, compared with that of the NO x  adsorption material according to Reference Example No. 2 using the mordenite, when it underwent the ion-exchange processing in which it was heated to 400° C., and therefore the usefulness of the present invention becomes apparent by taking the aforementioned examples into account. 
     INDUSTRIAL APPLICABILITY 
     In addition to putting the NO x  adsorption material according to the present invention in place on the exhaust-gas upstream side of NO x  storage-and-reduction type catalyst to use, it is also feasible to use it independently.