Patent Publication Number: US-2011064633-A1

Title: Multi-Functional Catalyst Block and Method of Using the Same

Description:
BACKGROUND 
     1. Technical Field 
     The present invention relates to a multi-functional catalyst block for reducing waste materials from the exhaust of a combustion engine. 
     2. Background Art 
     Like gasoline engines, diesel engines have been widely used for transportation and many other stationary applications. A combustion exhaust from diesel engines often contains a variety of combustion waste materials including unburned hydrocarbon (HC), carbon monoxide (CO), particulate matter (PM), nitric oxide (NO), and nitrogen dioxide (NO 2 ), with NO and NO 2  collectively referred to as nitrogen oxide or NO x . Removal of CO, HC, PM, and NO x  from the combustion exhaust is needed for cleaner emissions. The combustion exhaust treatment becomes increasing important in meeting certain emission requirements. 
     Conventional emission control systems often use separate devices for the reduction of NO x  and particulate matter. For example, a singular SCR (selective catalytic reduction) catalyst is used for converting NO x  to nitrogen (N 2 ) and a singular particulate filter (PF) is used for removing particulate matter. 
     However, conventional emission control systems have met with limited use as they lack, among other things, concurrent and balanced consideration for emission control efficiency and space conservation. 
     There is a continuing need to provide an emission control system with features more suitable for meeting increasingly stringent industry and environmental standards. 
     SUMMARY 
     According to one aspect of the present invention, there is provided a multi-functional catalyst block for reducing waste materials in the exhaust from a combustion engine. In one embodiment, the multi-functional catalyst block includes a substrate, a urea-hydrolyzing catalyst supported on the substrate, and a selective catalytic reduction (SCR) catalyst supported on the substrate. 
     In another embodiment, the substrate is a configured as a wall-flow particulate filter. In yet another embodiment, the substrate is configured as a flow-through device. 
     In yet another embodiment, the multi-functional catalyst block is provided with a first zone and a second zone downstream of the first zone relative to the combustion engine, wherein at least 90 weight percent of the urea-hydrolyzing catalyst is located in the first zone and at least 90 weight percent of the SCR catalyst is located in the second zone. In yet another embodiment, the urea-hydrolyzing catalyst and the SCR catalyst form a mixture on the substrate. 
     According to another aspect of the present invention, an emission control system is provided for reducing waste materials transported in an exhaust passage from a combustion engine. In one embodiment, the emission control system contains the multi-functional catalyst block described herein. In another embodiment, the emission control system further includes an oxidation catalyst disposed downstream of the engine and upstream of the multi-functional catalyst block. In yet another embodiment, the emission control system further includes an oxidation catalyst disposed downstream of the multi-functional catalyst block. 
     According to yet another aspect of the present invention, a method is provided for reducing waste materials in the exhaust of a combustion engine. In one embodiment, the method includes contacting the exhaust with a reductant and a multi-functional catalyst block as described herein to form a treated exhaust. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  schematically depicts an emission control system having a multi-functional catalyst block according to various embodiments of the present invention; 
         FIG. 2  schematically depicts an emission control system having a multi-functional catalyst block coupled with one or more oxidation catalyst according to various embodiments of the present invention; 
         FIG. 3A  depicts an enlarged view of a section of the multi-functional catalyst block; and 
         FIG. 3B  is a view similar to  FIG. 3A  illustrating another embodiment of the multi-functional catalyst block. 
     
    
    
     DETAILED DESCRIPTION 
     As required, detailed embodiments of the present invention are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for the claims and/or a representative basis for teaching one skilled in the art to variously employ the present invention. 
     Moreover, except where otherwise expressly indicated, all numerical quantities in the description and in the claims are to be understood as modified by the word “about” in describing the broader scope of this invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary, the description of a group or class of material as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more members of the group or class may be equally suitable or preferred. 
     As a matter of definition, and when used in this detailed description and in the claims: 
     “SCR” means selective catalytic reduction and includes a reducing catalyst which speeds or enhances a chemical reduction of NO x  through the assistance of a reductant during lean operation; 
     “DPF” or “DF” refers to the particulate filter employed to remove particulate matter or the like; 
     “NO x ” means nitrogen oxide and illustratively includes a mixture of compounds of nitric oxide (NO) and nitrogen dioxide (NO 2 ); 
     “Urea poisoning” means catalyst deactivation due to accumulation of urea molecules on the catalyst and may be manifested by the formation of undesirable urea derived byproducts; and 
     “Catalyst deactivation” means catalytic activity reduction due to urea poisoning, or reduction in NO x  conversion in the case for SCR catalyst. 
     Emission control systems typically use selective catalytic reduction (SCR) catalysts to convert certain waste materials such as NO x  to form less harmful counterparts such as N 2 , for safer emissions. Ammonia is a commonly used reductant for SCR catalyst catalyzed NO x  conversion. Decomposition of urea and subsequent reduction of NO x  typically occurs according to the following scheme: 
     Urea decomposition: 
     
       
         
         
             
             
         
       
     
     NO x  reduction: 
       4NO+4NH 3 +O 2 →4N 2 +6H 2 O
 
       6NO 2 +8NH 3 →7N 2 +12H 2 O
 
       2NH 3 +NO+NO 2 →2N 2 +3H 2 O
 
     Ammonia is often supplied by hydrolysis of liquid urea. Supply of the urea into the emission control system should be both time and amount controlled such that the urea is not present in substantial excess. Excess urea can be detrimental to the emission control system as excess urea can form urea deposits on and around catalysts, particularly SCR catalysts, and induce catalyst deactivation. 
     The present invention is capable of reducing waste materials from the exhaust of an internal combustion engine such as a diesel engine or a gasoline engine. Examples of the waste materials include unburned hydrocarbon (HC), carbon monoxide (CO), particulate matters (PM), nitric oxide (NO), and nitrogen dioxide (NO 2 ), with NO and NO 2  collectively referred to as nitrogen oxide or NO x . 
     With respect to the Figures that will be described in detail below, like numerals are used to designate like structures throughout the Figures. 
     According to at least one aspect of the present invention, an emission control system, as generally shown at  100  in  FIG. 1 , is provided for reducing waste materials from the exhaust of an internal combustion engine. The emission control system  100  includes an exhaust passage  102  and a multi-functional catalyst block  106 . As collectively shown in  FIG. 1  and  FIGS. 3A-3B , the multi-functional catalyst block  106  includes a urea-hydrolyzing catalyst  314  and a SCR catalyst  312 , with both supported on a substrate generally shown at  318  having wall portions  316 . Use of the multi-functional catalyst block  106 , being a stand-alone or discrete unit, as described in more detail below, is believed to provide at least one of the following advantages: reduced catalyst deactivation due to urea poisoning, increased NOx conversion at lower temperatures, reduced exhaust backpressure and improved fuel economy, and reduced overall system complexity and improved vehicle packaging. 
     While not intended to be limited by any theory, one possible mechanism by which the multi-functional catalyst block is resistant to urea poisoning may be that the SCR catalyst is protected from the harmful effects, such as the formation of polymeric byproducts, of urea deposits as excess urea is hydrolyzed and hence reduced; and more catalytic sites of the SCR catalyst are made available for NO x  conversion reactions. In addition, the catalyst material for the urea-hydrolyzing catalyst  314  is advantageously chosen and designed to have little or no impairment on the catalytic function of the SCR catalyst  312 . 
     Several suitable variations can be had with respect to the multi-functional catalyst block  106  depending upon particular application needs at hand. For instance, and as depicted in  FIGS. 3A-3B , the multi-functional catalyst block  106  can be configured as a wall-flow particulate filter having thereupon the urea-hydrolyzing catalyst  314  and the SCR catalyst  312 , wherein the substrate  318  have relevant ends  308  plugged to force an exhaust  117  to flow in the direction of AA via the wall portions  316 . Alternatively, the multi-functional catalyst block  106  can be configured as flow-through having thereupon the SCR catalyst  312  and the urea-hydrolyzing catalyst  314 . In this latter variation, one or more particulate filters may be independently coupled to, either upstream or downstream of, the multi-functional catalyst block  106 , for the removal of particulate matters. 
     It has been found that, the multi-functional catalyst block  106  as contemplated herein provides a synergistically broadened catalytic temperature range and hence enhanced NO x  reduction efficiency in comparison to existing configurations, in part due to the fact that there is less impact of urea poisoning and hence less reduction thereof on NO x  conversion. Moreover, the SCR catalyst is made more available for the NO x  conversion reactions and the use no longer has to be diluted for urea hydrolysis as the latter is now compensated for by the inclusion of urea-hydrolyzing catalyst in the catalyst block  106 . 
     It has further been found that, the multi-functional catalyst block  106  as applied in an emission control system such as one shown at  100  in  FIG. 1 , can provide substantial space reduction in a range of 10 to 40 percent relative to conventional systems. 
     In at least one embodiment, and as shown in FIGS.  1  and  3 A- 3 B, the multi-functional catalyst block  106  is a wall-flow particulate filter having thereupon the urea-hydrolyzing catalyst  314  and the SCR catalyst  312 . 
     Both catalysts can be disposed on the particulate filter in various ways. For instance, and as illustratively depicted in  FIG. 3A , there is provided an enlarged cross-sectional view of the multi-functional catalyst block  106  in one variation. As shown in  FIG. 3A , the multi-functional catalyst block  106  has a first zone  302  and a second zone  304 . The second zone  304  is downstream of the first zone  302  as viewed from the location of the engine  112 . The first and the second zones  302 ,  304  preferably sequentially align along the flow direction AA and therefore separate from each other. However, a clean-cut boundary is not necessarily required between the two zones  302 ,  304  and an incidental overlap of catalyst composition at the boundary does not affect the general practice of the invention. 
     In one variation, at least 60 percent, 70 percent, or 90 percent by weight of the urea-hydrolyzing catalyst  314  as present on the multi-functional catalyst block  106  is located in the first zone  302 . In another variation at least 60 percent, 70 percent, 80 percent or 90 percent by weight of the SCR catalyst  312  as present on the multi-functional catalyst block  106  is located in the second zone  304 . 
     The volume ratio between the first zone  302  and the second zone  304  can be adjusted such that the urea-hydrolyzing activities of the urea-hydrolyzing catalyst  314  and the NO x  conversion activities of the SCR catalyst  312  can be coordinated depending upon a particular exhaust waste removal application at hand. In one variation, the volume ratio is from 1:10 to 10:1; from 1:5 to 5:1, from 3:10 to 10:3, from 2:5 to 5:2, or from 1:2 to 2:1. 
     The exhaust  117 , along with an introduced reductant  119 , such as urea for example, enters the multi-functional catalyst block  106  via entry channels  306  and exits via the wall portions  316  and subsequently exits via exit channels  310  to form a treated exhaust  117 ′, as respective ends  308  are plugged. 
     Because the urea-hydrolyzing catalyst  314  located in the first zone  302  is advantageously positioned upstream of the SCR catalyst  312  located in the second zone  304 , and because in this particular configuration, the flow of the exhaust  117  enters and exits via the wall portions  316  as described above, the majority of the reductant  119  as contained within the exhaust  117  is forced to contact the urea-hydrolyzing catalyst  314  in the first zone  302  to form ammonia via a forced interaction between the reductant  119  and the hydrolysis catalyst. 
     In this embodiment, several design parameters can be adjusted to ensure that the exhaust  117  has been substantially acted upon by the urea-hydrolyzing catalyst  314  prior to its contact with the SCR catalyst  312 . These parameters include, but are not limited to, an overall aspect ratio between length and diameter of the multi-functional catalyst block  106 , porosity of the substrate walls  316 , filter channel diameter, filter channel count, and coating ratio between the first and second zones  302 ,  304 . 
     The resultant ammonia is then available for the NO x  conversion reactions taking place in the second zone  304  which is more downstream of the first zone  302 . As the exhaust  117  enters into the exit channels  310  through the wall portions  316 , the majority of the urea, for instance, at least 50 percent, 60 percent, 70 percent, 80 percent, or 90 percent by weight, has been converted to ammonia via the forced interaction in the direction of the arrows shown. 
     Several advantages come with this design. For instance, the ammonia is “freshly” produced “in situ” from the reductant  119  right where it is needed for the SCR catalyst-assisted NO x  conversion. Secondly, the reductant  119  is forced into contact with the urea-hydrolyzing catalyst  314  within the limited open areas of the channels  306  and as a result, the majority, for instance, at least 50 percent, 60 percent, 70 percent, 80 percent, or 90 percent by weight, if not all, of the reductant  119  is effectively utilized for urea hydrolyzing to ammonia. The amount of unused urea is effectively reduced, and the SCR catalyst  312  is relatively protected from the detrimental effect of the unused urea. Moreover, the catalytic sites of the SCR catalyst do not have to be used for urea hydrolysis purposes, more catalytic sites of the SCR catalyst are made available for NO x  conversion reactions, and the catalyst block  106  can be made smaller in size than a conventional SCR catalyst. 
     The multi-functional catalyst block  106  can be provided with any suitable SCR catalyst loading concentration in grams per cubic inch of a loading volume, generally shown at “A” in  FIG. 1 . The loading concentration can be dependent upon the substrate porosity upon which the urea-hydrolyzing catalyst and the SCR catalyst are deposited. For instance, the SCR catalyst can have a loading concentration of 0.5 g/in 3  (grams per cubic inch) for lower porosity filters, and can have a loading concentration of 2 g/in 3  for higher porosity filters. In general and according to one or more embodiments of the present invention, the SCR catalyst loading concentration is in a range independently selected from no less than 0.1 g/in 3 , 0.2 g/in 3 , 0.3 g/in 3 , or 0.4 g/in 3 , to no greater than 4.0 g/in 3 , 3.5 g/in 3 , 3.0 g/in 3 , or 2.5 g/in 3 . 
     The multi-functional catalyst block  106  can be provided with any suitable urea-hydrolyzing catalyst loading concentration in grams per cubic inch of a loading volume, generally shown at “A” in  FIG. 1 . In certain instances, the urea-hydrolyzing catalyst  314  loading concentration is in a range independently selected from no less than 0.1 g/in 3 , 0.2 g/in 3 , 0.3 g/in 3 , or 0.4 g/in 3 , to no greater than 4.0 g/in 3 , 3.5 g/in 3 , 3.0 g/in 3 , or 2.5 g/in 3 . 
     In another variation, and as depicted in  FIG. 3B , the urea-hydrolyzing catalyst  314  and the SCR catalyst  312  can be combined to form a mixture, a homogeneous mixture in certain instances, with the catalyst mixture being supported on the substrate  318 . 
     Referring now back to  FIG. 1 , in the illustrated embodiment, the reductant  119  can be disposed within the exhaust passage  102  downstream of an engine  112 . An aperture  118  is optionally located on the exhaust passage  102  and disposed between the engine  112  and the multi-functional catalyst block  106  as described herein to facilitate the introduction of the reductant  119  into the exhaust passage  102 . The reductant  119 , for reducing NO x  to nitrogen N 2 , is introduced into the exhaust passage  102  optionally through a nozzle (not shown). The introduction of the reductant  119  is optionally achieved through the use of a valve  120  which can be employed to meter the desired amount of the reductant  119  into the exhaust  117  from source  104 . The exhaust  117  with the reductant  119  is then conveyed further downstream to along with the multi-functional catalyst block  106  for the reduction of NO x  and the removal of the particulate matter. 
     In yet another embodiment, the range of the distance between the aperture  118  and the multi-functional catalyst block  106  may be independently selected from a range of no less than 0.5 centimeters, 10 centimeters, 20 centimeters, 30 centimeters, 40 centimeters, 50 centimeters, 60 centimeters, or 70 centimeters, to no greater than 140 centimeters, 130 centimeters, 120 centimeters, 110 centimeters, 100 centimeters, 90 centimeters, or 80 centimeters. 
     The reductant  119  may be of any material suitable for reducing NO x  to a harmless, releasable substance such as nitrogen N 2 . The reductant  119  may include ammonia, liquid urea, solid urea, or combinations thereof. As is known, when exposed to a warm or hot exhaust, urea readily decomposes to ammonia. In certain embodiments, a molar ratio NH 3 /NO x  is typically kept at a value predesignated so as to minimize NH 3  slip past the catalysts and out into the air. An exemplary molar ratio of NH 3 /NO x  is at or near one. 
     The substrate  318  as contained within the multi-functional catalyst block  106  for supporting the urea-hydrolyzing catalyst  314  and the SCR catalyst  312  may be a monolith, which is generally described as a ceramic block made of a number of substantially parallel flow channels. The monolith may be made of ceramic materials such as cordierite, mullite, and silicon carbide or metallic materials such as iron chromium alloy, stainless steel, and Inconel®. The flow channels of the monolith may be of any suitable size, and in certain instances are of a size of 0.5 to 10 millimeters in diameter. The channels can be substantially straight, hollow, and parallel to the flow of the exhaust, therefore flow obstruction to the exhaust is minimized. In the event that the substrate  318  is configured as a wall-flow particulate filter for additionally removing the particulate matters, the substrate can further include cordierite, silicon carbide, metal fiber, paper, or combinations thereof. 
     In at least one embodiment, the SCR catalyst  312  is generally zeolite based. The term “zeolite” generally refers to an aluminosilicate framework containing atoms of oxygen aluminum and/or silicon. An example of a natural zeolite is mordenite or a chabazite. Synthetic zeolites illustratively include type A as synthetic forms of mordenite, type B as ZSM-5® zeolites, and type Y as ultra-stabilized Beta zeolite. The framework structure of the zeolites often acquires an overall negative charge compensated for by exchangeable cations which may readily be replaced by other cations such as metal cations through methods including ion exchange. 
     The SCR catalyst  312  can include an alkaline earth metal exchanged zeolite, precious metal exchanged zeolite such as platinum based and/or a base metal exchanged zeolite such as copper and iron based zeolites. While any type of zeolite may be used, some suitable zeolites include X-type zeolite, Y-type zeolite, and/or ZSM-5 type zeolite. 
     When used in the SCR catalyst  312 , the alkaline earth metal illustratively includes barium, strontium, and calcium. Suitable calcium sources for the alkaline earth metal include calcium succinate, calcium tartrate, calcium citrate, calcium acetate, calcium carbonate, calcium hydroxide, calcium oxylate, calcium oleate, calcium palmitate and calcium oxide. Suitable strontium sources for the alkaline earth metal include strontium citrate, strontium acetate, strontium carbonate, strontium hydroxide, strontium oxylate and strontium oxide. Suitable barium sources for the alkaline earth metal include barium butyrate, barium formate, barium citrate, barium acetate, barium oxylate, barium carbonate, barium hydroxide and barium oxide. 
     When used in the SCR catalyst  312 , the rare earth metal may illustratively include lanthanum, cerium, and/or neodymium. Suitable neodymium sources for the rare earth metal include neodymium acetate, neodymium citrate, neodymium oxylate, neodymium salicylate, neodymium carbonate, neodymium hydroxide and neodymium oxide. Suitable cerium sources for the rare earth metal include cerium formate, cerium citrate, cerium acetate, cerium salicylate, cerium carbonate, cerium hydroxide and cerium oxide. Suitable lanthanum sources for the rare earth metal include lanthanum acetate, lanthanum citrate, lanthanum salicylate, lanthanum carbonate, lanthanum hydroxide and lanthanum oxide. 
     The SCR catalyst  312  may be prepared by any suitable methods. In the event that hydrogen-ion-exchanged acid zeolites are used, active ingredients may be incorporated into the zeolites in a manner illustratively shown as follows. A starting material is produced, including the zeolites, by mixing, milling and/or kneading the individual components or their precursor compounds (for example water-soluble salts for the specified metal oxides) and if appropriate with the addition of conventional ceramic fillers and auxiliaries and/or glass fibers. The starting material is then either processed further to form unsupported extrudates or is applied as a coating to a ceramic or metallic support in honeycomb or plate form. 
     A binder is optionally used to bring together all ingredients to form the SCR catalyst. The binder is used to prevent dissolution and redistribution of the ingredients. Possible binders include acidic aluminum oxide, alkaline aluminum oxide, and ammonium aluminum oxide. In certain particular instances, a soluble alkaline aluminum oxide with a pH of at least 8 is used as the binder. 
     Examples of suitable SCR catalysts are described in U.S. Pat. No. 4,961,917 to Byrne, the entire contents of which are incorporated herein by reference. Some suitable compositions include one or both of an iron and a copper metal atom present in a zeolite in an amount of from about 0.1 to 30 percent by weight of the total weight of the metal atoms plus zeolite. Zeolites are relatively resistant to sufur poisoning and typically remain active during a SCR catalytic reaction. Zeolites typically have pore sizes large enough to permit adequate movement of NO x , ammonia, and product molecules N 2  and H 2 O. The crystalline structure of zeolites exhibits a complex pore structure having more or less regularly recurring connections, intersections, and the like. By way of example, suitable zeolites are made of crystalline aluminum silicate, with a silica to alumina ratio in the range of 5 to 400 and a mean pore size from 3 to 20 Angstroms. 
     Suitable SCR catalyst  312  to be used in the multi-functional catalyst block  106  can be of one composition, such as one composition of copper-containing zeolite or iron-containing zeolite; and can also be of a physical mixture of two or more catalysts in any suitable ratio. For instance, the SCR catalyst  312  can contain a mixture of Fe and Cu with any suitable weight ratio, for instance, of from 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, to 10:1. Alternatively, the SCR catalyst  312  used herein can be an iron-containing zeolite or a copper-containing zeolite combined with one or more other metals selected from the group consisting of vanadium, chromium, molybdenum, tungsten, or any combinations thereof. 
     The SCR catalyst  312  and the urea-hydrolyzing catalyst  314  can be coated onto the substrate using any suitable method. One exemplary method of such a coating is illustrated in U.S. Pat. No. 7,229,597 to Patchett et al., the entire contents of which are incorporated herein by reference. In essence, the particulate filter with a desired porosity is immersed in a catalyst slurry which is then allowed to dry under compressed air. This dipping-drying process may be repeated until the desired level of coating is achieved. After coating, the particulate filter may be dried at a temperature, such as 100 degrees Celsius, and subsequently calcined at a relatively higher temperature, such as in the range of 300 to  500  degrees Celsius. 
     Optionally, and as shown in  FIG. 2 , an oxidation catalyst  214  can be disposed within the exhaust passage  102  downstream of the engine  112  and upstream of the multi-functional catalyst block  106 . Oxidation catalysts that contain platinum group metals, base metals and combinations thereof help to promote the conversion of both hydrocarbon (HC) and carbon monoxide (CO) waste materials and at least some portion of the particulate matter through oxidation of these pollutants to carbon dioxide and water. The oxidation catalyst  214  generally helps to break down the waste materials in the exhaust to less harmful components. In particular, an exemplary oxidation catalyst  214  utilizes palladium and platinum catalysts to reduce the unburned hydrocarbon and carbon monoxide according to the following reaction formula: CO+O 2 →CO 2 . Removal of the HC and CO using the oxidation catalyst  214  helps to relieve some burden on the downstream staged catalyst unit  106  in remediating the exhaust. 
     In addition, the oxidation catalyst  214  also converts a certain portion of the nitric oxide (NO) to nitrogen dioxide (NO 2 ) such that the NO/NO 2  ratio is more suitable for downstream SCR catalytic reactions. An increased proportion of NO 2  in the NO x , due to the catalytic action of the upstream oxidation catalyst  214 , enhances the reduction of NO x  as compared to exhaust streams containing smaller proportions of NO 2  in the NO x  component. Furthermore, the oxidation catalyst  214  helps enable soot removal and regeneration of the particulate filter for continuous engine operation. 
     The emission control system  100  may be further altered in its configuration without materially changing its intended function. For instance, a second oxidation catalyst  224  can be disposed downstream of the multi-functional block  106 , as shown in  FIG. 2 . When used in concert with the first oxidation catalyst  214 , the second oxidation catalyst  224  mainly serves to oxidize ammonia molecules that may have slipped through the exhaust passage  102  and to convert the slipped ammonia molecules to N 2 . In addition, any unburned hydrocarbon that is left untreated may be oxidized at this point before final release into the air. 
     In at least one embodiment, the urea-hydrolyzing catalyst  314  contains at least one oxide. Examples of suitable oxides include titanium dioxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ), zirconium oxide (ZrO 2 ), sulfur oxide (SO 3 ), tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), aluminum oxide, yttrium oxide, nickel oxide, cobalt oxide, or combinations thereof. Without being limited by any theory, the oxide contained within urea-hydrolyzing catalyst  314  functions at least partially as hydrolyzation molecules that induce the hydrolyzation and hence breakdown of the excess urea and resultant alleviation of the deactivating effects of the excess urea. 
     The urea-hydrolyzing catalyst  314  can be applied to the multi-functional catalyst block  106  through any suitable methods. For instance, a precursor substance for forming the urea-hydrolyzing catalyst  314  is powdered, made into an aqueous slurry and then milled. The precursor substance is preferably provided in an amount such that a stoichiometric amount of ammonia can be generated based on the action of the urea-hydrolyzing catalyst  314  to be in alignment with the NO x  conversion reactions. The amount for the precursor substance can be determined by experiment or else be calculated based on the molecular weight and/or solubility of the particular precursor substance used. As a result, the urea-hydrolyzing catalyst  314  is formed such that a pre-determined effectiveness of the SCR catalyst  312  is achieved in the reduction of NO x  in NO x -containing waste materials. 
     The urea-hydrolyzing catalyst  314  produced in this way helps to impart a considerable long-term hydrothermal stability to the SCR catalyst  312  against the influence of urea poisoning. For example, the SCR activity of the multi-functional catalyst block  106  is not impaired by urea poisoning even after aging for 18 to 36 hours at 800 degrees Celsius or higher. 
     Suitable zirconium sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include zirconium dioxide, zirconium oxychloride, zirconium tert-butoxide, zirconium ethoxide, zirconium isopropoxide, and colloidal zirconium oxide. 
     Suitable titanium sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include titanium dioxide, titanium oxychloride, titanium oxynitrate, titanium isobutoxide, titanium n-butoxide, titanium tert-butoxide, titanium ethoxide, titanium isopropoxide, titanium methoxide, titanium n-propoxide, and colloidal titanium oxide. 
     Suitable aluminum sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include aluminum oxide, aluminum hydroxide, aluminum methoxide, aluminum n-butoxide, aluminum ethoxide, and aluminum isopropoxide. 
     Suitable silicon sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include silicon oxide and colloidal silicon oxide. 
     Suitable yttrium sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include yttrium oxide, colloidal yttrium oxide, and yttrium isopropoxide. 
     Suitable nickel sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include nickel oxide and nickel hydroxide. 
     Suitable cobalt sources of the precursor substance for the urea-hydrolyzing catalyst  314  generally include cobalt oxide and cobalt hydroxide. 
     According to at least another aspect of the present invention, a method is provided for reducing waste materials from the exhaust of an internal combustion engine. In one embodiment, the method includes contacting the exhaust with the multi-functional catalyst block  106  as described herein. In another embodiment, the method further includes contacting the exhaust with an oxidation catalyst  214 ,  224 , prior to and or after the step of contacting the exhaust with the multi-functional catalyst block  106 . 
     While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.