Abstract:
Disclosed here are methods of preparing zero platinum group metal catalysts systems with different support oxide material. A ZPGM catalyst system may include a substrate and a washcoat and an impregnation layer, wherein said impregnation layer may include the ZPGM pervoskite catalyst and the washcoat layer may include the support oxides material. Suitable support oxides material may include ZrO 2 , ZrO 2  doped with lanthanide group metals, Nb 2 O 5 , Nb 2 O 5 —ZrO 2 , Al 2 O 3  and Al 2 O 3  doped with lanthanide group metals, TiO 2  and doped TiO 2  or mixtures thereof.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Application No. 61/791,721, filed Mar. 15, 2013, titled Methods for Oxidation and Three-way ZPGM Catalyst Systems and Apparatus Comprising Same and is a continuation-in-part of U.S. application Ser. No. 13/856,896, filed Apr. 4, 2013, titled System and Method for Two and Three Way Mixed Metal Oxide ZPGM Catalyst, and is related to U.S. application Ser. No. 13/849,185, filed Mar. 22, 2013, titled ZPGM Catalyst Systems and Methods of Making Same and to U.S. application Ser. No. 13/891,647, filed May 10, 2013, titled ZPGM Diesel Oxidation Catalysts and Methods of Making and Using Same, the entireties of which are incorporated herein by reference as if set forth herein. 
    
    
     BACKGROUND 
     1. Technical Field 
     This disclosure relates generally to catalytic converters and, more particularly to catalytic converters which are free of any platinum group metals. 
     2. Background Information 
     Emission standards for unburned contaminants, such as hydrocarbons, carbon monoxide and nitrogen oxide, continues to become more stringent. In order to meet such standards, diesel oxidation catalysts are used in the exhaust gas lines of internal combustion engines. These catalysts promote the oxidation of unburned hydrocarbons and carbon monoxide as well as the oxidation of nitrogen oxides in the exhaust gas stream to reduce the engine generated pollutants. One of the major limitations of current catalysts is that the Platinum Group Metals (PGM) used in their fabrication have very high demand and increasing prices. 
     Therefore, there is a continuing need to provide cost effective catalyst systems that provide sufficient conversion so that HC, NOx, and CO emission standards can be satisfied. 
     SUMMARY 
     Diesel Oxidation ZPGM catalyst systems are disclosed. ZPGM catalyst systems may oxidize toxic gases, such as carbon monoxide, hydrocarbons and nitrogen oxides that may be included in exhaust gases. 
     In one embodiment, ZPGM catalyst systems may oxidize NO to NO 2  which may be used for the oxidation of carbon soot. 
     ZPGM catalyst converters may include: a substrate, a washcoat, and an impregnation layer. Washcoats may include at least support oxides material and may include ZPGM catalysts. Impregnation layers may include ZPGM catalysts. 
     Suitable known in the art chemical techniques, deposition methods and treatment systems may be employed to form the disclosed ZPGM catalyst systems. 
     Suitable materials for use as substrates may include cordierite, metallic alloys, foams, microporous materials, zeolites or combinations. 
     Materials suitable for use as ZPGM catalysts include Lanthanum (La), Silver (Ag), Manganese (Mn) and combinations thereof. The disclosed ZPGM DOC systems may include perovskite structures with the characteristic formulation ABO 3  or related structures. 
     Support oxide materials of use in catalysts containing one or more of the aforementioned combinations may also include ZrO 2 , doped ZrO 2  with Lanthanide group metals, Nb 2 O 5 , Nb 2 O 5 —ZrO 2 , alumina and doped alumina, TiO 2  and doped TiO 2 . 
     Type of support oxide material in ZPGM catalyst system significantly influences the performance of ZPGM catalyst with perovskite structure La 1-x Ag x MnO 3  under diesel oxidation condition. 
     Numerous other aspects, features and advantages of the present disclosure may be made apparent from the following detailed description, taken together with the drawing figures. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       Embodiments of the present disclosure are described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. Unless indicated as representing prior art, the figures represent aspects of the present disclosure. 
         FIG. 1  shows ZPGM catalyst system structures, according to an embodiment. 
         FIG. 2  is a flowchart of a method of preparation of a ZPGM catalyst, according to an embodiment. 
         FIG. 3  shows DOC light-off test results of a ZPGM catalyst system, according to an embodiment. 
         FIG. 4  shows SOC light-off test results of a ZPGM catalyst system, according to an embodiment. 
     
    
    
     DETAILED DESCRIPTION 
     In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, which are not to scale or to proportion, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings and claims, are not meant to be limiting. Other embodiments may be used and/or and other changes may be made without departing from the spirit or scope of the present disclosure. 
     DEFINITIONS 
     As used here, the following terms have the following definitions: 
     “Exhaust” refers to the discharge of gases, vapor, and fumes including hydrocarbons, nitrogen oxide, and/or carbon monoxide. 
     “Impregnation” refers to the process of totally saturating a solid layer with a liquid compound. 
     “Wash-coat” refers to at least one coating including at least one oxide solid that may be deposited on a substrate. 
     “Conversion” refers to the chemical alteration of at least one material into one or more other materials. 
     “T50” refers to the temperature at which 50% of a material is converted. 
     “Oxidation Catalyst” refers to a catalyst suitable for use in oxidizing at least hydrocarbons and carbon monoxide. 
     “Zero Platinum Group (ZPGM) Catalyst” refers to a catalyst completely or substantially free of platinum group metals. 
     “Platinum Group Metals (PGMs)” refers to platinum, palladium, ruthenium, iridium, osmium, and rhodium. 
     DESCRIPTION OF THE DRAWINGS 
     Various example embodiments of the present disclosure are described more fully with reference to the accompanying drawings in which some example embodiments of the present disclosure are shown. Illustrative embodiments of the present disclosure are disclosed herein. However, specific structural and functional details disclosed herein are merely representative for purposes of describing example embodiments of the present disclosure. This disclosure however, may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein. 
     System Configuration and Composition 
       FIG. 1  depicts ZPGM catalyst system  100  configurations, according to various embodiments. As shown in  FIG. 1A , ZPGM catalyst system  100  may include a substrate  102 , a washcoat  104 , and an impregnation layer  106 , where washcoat  104  or impregnation layer  106 , or both, may contain active oxidation ZPGM catalyst components.  FIG. 1B  shows an embodiment of ZPGM catalyst system  100  that includes a substrate  102  and a washcoat  104  only, where washcoat  104  may include the active oxidation ZPGM catalyst components. 
     According to an embodiment, ZPGM catalyst system  100  may include a perovskite structure having the general formula ABO 3  or related structures resulting from the partial substitution of the A site. Partial substitution of the A site with M element will yield the general formula A 1-x M x BO 3 . “A” may include yttrium, lanthanum, strontium, or mixtures thereof. “B” may include a single transition metal, including manganese, cobalt, chromium, or a mixture thereof. M may include silver, iron, Cerium, niobium or mixtures thereof; and “x” may take values between 0 and 1. The perovskite or related structure may be present in about 1% to about 30% by weight. 
     Methods of Preparation of Washcoat and Impregnation Layers 
       FIG. 2  illustrates method for preparation  200  of ZPGM catalyst system  100 , according to an embodiment. 
     In one embodiment, method for preparation  200  may be a two-step process.  FIG. 2  A is a washcoat  104  preparation process. In this process, components of washcoat  104  may undergo a milling  202  process in which washcoat  104  materials may be broken down into smaller particle sizes; the mixture may include water, a suitable binder material and a support oxide material or OSM, or both. Suitable support oxide material may include ZrO 2 , doped ZrO 2  with Lanthanide group metals, Nb 2 O 5 , Nb 2 O 5 —ZrO 2 , Al 2 O 3  and doped Al 2 O 3 , TiO 2  and doped TiO 2  or mixtures thereof. After milling  202  process, an aqueous slurry may be obtained. Milling  202  process may take from about 10 minutes to about 10 hours, depending on the batch size, kind of material and particle size desired. In one embodiment of the present disclosure, suitable average particle size (APSs) of the slurry may be of about 4 microns to about 10 microns, in order to get uniform distribution of washcoat  104  particles. Finer particles may have more coat ability and better adhesion to substrate  102  and enhanced cohesion between washcoat  104  and impregnation layers  106 . Milling  202  process may be achieved by employing any suitable mill such as vertical or horizontal mills. In order to measure exact particle size desired during milling  202  process, laser light diffraction equipment may be employed. 
     After milling  202  process the aqueous slurry may be coated onto a suitable substrate  102  in washcoating  204  step. In this step, the aqueous slurry may be placed on substrate  102  in any suitable manner. For example, substrate  102  may be dipped into the slurry, or the slurry may be sprayed on substrate  102 . Other methods of depositing the slurry onto substrate  102  known to those skilled in the art may be used in alternative embodiments. If substrate  102  is a monolithic carrier with parallel flow passages, a washcoat  104  may be formed on the walls of the passages. Followed by a drying  206  step, in which the washcoated substrate  102  may be dried at room temperature. Afterwards, the washcoated substrate  102  may undergo a firing  208  stage, in which the washcoated substrate  102  may be fired at a temperature ranging from 400° C. to 700° C., for approximately 2 hours to 6 hours. 
       FIG. 2  B is a flowchart of an impregnation preparation method. The process may start with first mixing  210  step, where a lanthanum nitrate solution may be added to a manganese nitrate solution and the solutions may be mixed for a suitable amount of time at room temperature. In some embodiments first mixing  210  process may last from 1 hour to 5 hours. Afterwards, during addition of metal  212  step, a silver nitrate solution or other suitable metal solutions may be added to the mixture of lanthanum nitrate and manganese nitrate; then the solution may be mixed at room temperature for about 1 hour to 5 hours, during second mixing  214 . When the mixture is ready, it may undergo impregnation  216  process, where the mixture may be impregnated onto a previously washcoated substrate  102 . Subsequently, impregnated substrate  102  may be subjected to a drying  218  process and a firing  220  process. Firing  220  process may last between 3 hours and 6 hours, and may be performed and a temperature between 600° C. and 800° C. 
     Various amounts of washcoats  104  and impregnation layers  106  may be coupled with a substrate  102 , preferably an amount that covers most of, or all of, the surface area of a substrate  102 . In an embodiment, about 60 g/L to about 250 g/L of a washcoat  104  may be coupled with a substrate  102 . 
     Other components such as acid or base solutions or various salts or organic compounds may be added to the aqueous slurry to adjust the rheology of the slurry and enhance binding of the washcoat  104  and impregnation layer  106  to the substrate  102 . 
     EXAMPLES 
     In example #1, a ZPGM catalyst system  100  including a ZPGM perovskite catalyst having a cordierite substrate  102 , a washcoat  104  and an impregnation layer  106  is prepared. Where washcoat  104  includes Praseodymium-doped Zirconium oxide, ZrO 2 —Pr 6 O 11 . ZrO 2 —Pr 6 O 11  is used as support oxide material which contains ZrO 2  from 80 to 95 percent by weight, preferably 90 percent by weight and Pr 6 O 11  from 5 to 20 percent by weight, preferably 10 percent by weight. Catalyst system is free of OSM material. Washcoat  104  may include a binder or small amount rheology adjustment additives. Rheology adjustment additives may include acids, among other suitable substances. Following deposition of washcoat, heat treatment may be performed at about 550° C. and may last from about 4 hours. The washcoat loading may be about 80 g/L to about 180 g/L, preferably 120 g/L. The impregnation layer  106  includes at least lanthanum, silver and manganese. This catalyst system is free of any oxygen storage material. The lanthanum in impregnation layer  106  is present in about 10% to about 40%, by weight. The silver in impregnation layer  106  is present in about 1% to about 10%, by weight. The manganese in impregnation layer  106  is present in about 10% to about 30%, by weight. After impregnation  216  the ZPGM catalyst system  100  may be heat treated at about 750° C. for about 4 hours. The resulting ZPGM catalyst system  100  has a perovskite structure La 1-x Ag x MnO 3 . 
       FIG. 3  shows the light-off test results  300  for the ZPGM catalyst system  100  of example #1 for a fresh sample. The light-off test is performed under simulated Diesel exhaust. Feed stream includes of 150 ppm NO, 1500 ppm of CO, 430 ppm of C 3 H 6  as hydrocarbon, 4% CO 2 , 4% of H 2 O and 14% of oxygen. The test is performed by increasing the temperature from about 100° C. to 400° C. at a constant rate of 20° C./min. The light-off test results  300  show that T50 for CO may be at about 273° C., T50 for HC may be at about 318° C. and T50 for NO may be at about 328° C. The NO conversion is result of oxidation of NO to NO 2 . Neither NH 3  nor N 2 O formed during reaction. 
     In example #2, a ZPGM catalyst system  100  including a ZPGM perovskite catalyst having a cordierite substrate  102 , a washcoat  104  and an impregnation layer  106  is prepared. Where washcoat  104  includes Lanthanum-doped alumina, Al 2 O 3 —La 2 O 3 . Al 2 O 3 —La 2 O 3  is used as support oxide material which contains Al 2 O 3  from 80 to 95 percent by weight, preferably 90 percent by weight and La 2 O 3  from 5 to 20 percent by weight, preferably 10 percent by weight. Catalyst system is free of OSM material. Washcoat  104  may include a binder or small amount rheology adjustment additives. Rheology adjustment additives may include acids, among other suitable substances. Following deposition of washcoat, heat treatment may be performed at about 550° C. and may last from about 4 hours. The washcoat loading may be about 80 g/L to about 180 g/L, preferably 120 g/L. The impregnation layer  106  includes at least lanthanum, silver and manganese. This catalyst system is free of any oxygen storage material. The lanthanum in impregnation layer  106  is present in about 10% to about 40%, by weight. The silver in impregnation layer  106  is present in about 1% to about 10%, by weight. The manganese in impregnation layer  106  is present in about 10% to about 30%, by weight. After impregnation  216  the ZPGM catalyst system  100  may be heat treated at about 750° C. for about 4 hours. The resulting ZPGM catalyst system  100  has a perovskite structure La 1-x Ag x MnO 3 . 
       FIG. 4  shows the light-off test results  400  for the ZPGM catalyst system  100  of example #2 for a fresh sample. The light-off test is performed under simulated Diesel exhaust condition. Feed stream includes of 150 ppm NO, 1500 ppm of CO, 430 ppm of C 3 H 6  as hydrocarbon, 4% CO 2 , 4% of H 2 O and 14% of oxygen. The test is performed by increasing the temperature from about 100° C. to 400° C. at a constant rate of 20° C./min. The light-off test results  400  show that T50 for CO may be at about 343° C., T50 for HC may be at about 388° C. and T50 for NO may be at about 398° C. The NO conversion is result of oxidation of NO to NO 2 . Neither NH 3  nor N 2 O formed during reaction. 
     Comparison of DOC light-off test results of ZPGM catalysts of Example#1 and Example#2 shows the type of support oxide material in ZPGM catalyst system significantly influences the activity of ZPGM catalyst with perovskite structure La 1-x Ag x MnO 3  under Diesel oxidation condition. Doped-ZrO 2  support shows superior activity in CO, HC and NO oxidation compare to doped-Al 2 O 3  support.