Patent Application
20160158699
The subject matter described herein relates to a catalyst system which facilitates the reduction of nitrogen oxides in vehicle exhaust gases, and more particularly to a catalyst system which reduces nitrous oxide (N2O) emissions from vehicle exhaust gases.
Environmental regulations pertaining to the reduction of emissions from vehicular engines are becoming increasingly stringent, requiring new designs to address the challenges of producing ever cleaner vehicles. Catalysts have long been used in the exhaust systems of automotive vehicles to convert carbon monoxide, hydrocarbons, and nitrogen oxide (NOx) pollutants into more environmentally benign gases such as carbon dioxide, water vapor, and nitrogen. It has long been known that so-called three-way catalysts (TWC) can be used to simultaneously convert carbon monoxide, hydrocarbons, and nitrogen oxides into more environmentally benign gases. Generally, such TWCs include a plurality or multiple precious metals such as platinum group metals (PGMs). For example, catalysts comprised of combinations of rhodium (Rh) and platinum (Pt) or palladium (Pd) have been used in TWC systems. Generally, it is believed that Pd is more effective to convert CO and HC, while Rh is more effective to reduce NOx compounds.
Oxides of nitrogen are of an increasing environmental concern. For example, the National Research Council in a 2010 study estimated that N2O molecules released into the atmosphere stay intact for an average of 120 years, and the environmental impact of one pound of N2O on atmospheric warming is over 300 times that of one pound of carbon dioxide. Increasingly stringent fuel economy standards exacerbate the production of NOx in vehicles.
Thus, it is preferable to operate vehicle engines under lean conditions, i.e., conditions where the air/fuel ratio is greater than stoichiometric to improve fuel efficiency and lower CO2 emissions. However, while lean operation improves fuel economy, such operation increase the difficulty of treating and removing NOx gases from vehicle exhaust systems. This has resulted in vehicle manufacturers developing so-called lean NOx traps which add to the complexity and cost of exhaust systems in an attempt to capture and reduce as much of the NOx as possible.
Other conditions encountered during normal operation of motor vehicles also result in the production of excess NOx gases. For example, during cold start-up of engines, the effectiveness and efficiency of the catalysts is reduced until the catalysts reach their light-off temperature. During vehicle acceleration, the increased flow of exhaust gases containing NOx and CO result in incomplete reduction of NOx compounds to N2 and cause additional N2O to be generated in the catalytic converter.
Accordingly, a need remains in this art to provide more efficient catalyst systems that are able to address and control emissions of pollutant gases over a wide range of operating conditions.
Those needs are addressed by embodiments of the present invention that provide a catalyst system which facilitates the reduction of nitrogen oxides in vehicle exhaust gases, and more particularly to a catalyst system which reduces nitrous oxide (N2O) emissions from vehicle exhaust gases.
In accordance with one embodiment of the present invention, a catalyst system for reducing N2O emissions in the exhaust system of a vehicle is provided and comprises a support in communication with the exhaust gas stream, with the support including an exhaust gas inlet and an exhaust gas outlet. The support has at least one exhaust gas passage therethrough. The support, which may be in the form of a monolithic, multi-cell honeycomb construction, comprises a first catalytic zone and a second catalytic zone positioned downstream from the first zone. The first catalytic zone includes a platinum group metal (PGM) catalyst comprising from about 50 to about 100 wt % rhodium, with the remainder comprising platinum and/or palladium in any weight ratio. The catalytic second zone includes a PGM catalyst comprising from about 50 to about 100 wt % palladium, with the remainder comprising platinum and/or rhodium in any weight ratio. By “PGM catalyst,” we mean either rhodium, platinum, or palladium, and mixtures thereof. Preferably, the support comprises cerium oxide, zirconium oxide, aluminum oxide, and mixtures thereof in any weight ratio.
In some embodiments, the second catalytic zone includes a nickel-copper catalyst which aids in further reducing any N2O still present in the exhaust system. In some embodiments, the nickel-copper catalyst comprises about 50 wt % nickel and about 50 wt % copper.
In another embodiment, the catalyst system includes a third catalytic zone downstream from the second catalytic zone, with the nickel and copper catalyst being located in the third catalytic zone. In embodiments that include three catalytic zones, the system may be configured such that the first catalytic zone in the exhaust gas passage comprises an inlet channel having first and second ends, with the first end of the inlet channel communicating with the exhaust gas inlet. The second catalytic zone comprises an outlet channel having first and second ends, with the second end of the outlet channel communicating with the exhaust gas outlet. The third catalytic zone comprises an intermediate channel having first and second ends, with the first end of said intermediate channel communicating with the second end of the inlet channel and the second end of the intermediate channel communicating with the first end of the outlet channel. The intermediate channel is oriented such that the flow of exhaust gas through the at least one exhaust gas passage is reversed from the direction of flow in the inlet and outlet channels.
Accordingly, it is a feature of the present invention to reduce nitrogen oxides in vehicle exhaust gases, and more particularly to a catalyst system which reduces nitrous oxide (N2O) emissions from vehicle exhaust gases. Other features and advantages of the present invention will be apparent from the following detailed description, the accompanying drawings, and the appended claims.
The following detailed description of specific embodiments of the present invention can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:
The gases found in most automotive vehicle exhausts contain only very small amounts of nitrous oxide (N2O) generated during fuel combustion in the engine. Rather, a problem is that N2O is formed by the catalysts in the vehicle exhaust system during different modes of operation. Nitrous oxide is formed when a vehicle is operated under lean conditions, i.e., hydrocarbon fuel is combusted in an excess of oxygen/air. While lean operating conditions provide advantages such as improved fuel efficiency and lower CO2 emissions, such operation increases the formation of nitrogen oxides (NOx). Typically, manufacturers have used lean NOx traps containing catalysts to absorb NOx compounds followed by NOx reduction when the engine is operated under rich (i.e., excess of fuel to air/oxygen) conditions. Alternatively, NOx reduction is accomplished by injecting a reductant such as ammonia into the exhaust gas stream.
We have determined that operating under lean, as well as rich, conditions contributes to N2O formation by conventional three-way catalysts typically used in vehicle exhaust systems. The NOx compounds that are treated when the engine is operated under lean conditions are only partially reduced by the catalysts when rich conditions or a reductant are imposed. Because conditions in the vehicle exhaust system can vary, the progression of NOx reduction is affected by the relative amounts and types of reductant (H2 and CO), the reaction residence time (space velocity of the exhaust gas, defined as exhaust gas flow rate divided by catalyst volume), and temperature of the exhaust gas. When the vehicle is not fully warmed up, or when the vehicle accelerates and exhaust gas space velocity increases, N2O rather than N2 is formed because the catalysts are able only to partially reduce the NOx gases.
When a vehicle accelerates, conditions in the exhaust system change. These changes include a higher exhaust flow rate, a higher mass of NO, and higher CO levels. During such challenging events, typical three way catalyst (TWC) formulations currently in use are overwhelmed. The result is that the TWC is able only to partially reduce NO, generating more N2O instead of fully reducing NO to N2.
Increased space velocity of the exhaust gas during vehicle acceleration also contributes to the problem of N2O formation by lowering the temperature of the catalyst to below its optimal active state. It is during this lowered active state of the three way catalyst where the majority of N2O is generated. Current TWC formulations principally are comprised of Pd. However, CO in the exhaust gas stream can poison Pd and result in the light-off temperature of the catalyst (defined as the temperature at which the catalyst converts at least 50% of unburned hydrocarbon emissions) being raised. This further extends the time during which the TWC is in such a lowered active state and results in the generation of N2O over a wider temperature range along with significant accumulation of N2O in the exhaust gases leaving the system.
Referring initially to
The first support 14 typically has a high precious metal loading, such as, for example, 68 g/ft3 of Pd and 2 g/ft3 of Rh, for a total precious metal loading of 70 g/ft3. As shown in
The second support 16 is located downstream from the first support 14 and is present to aid in controlling emissions during high mass flux situations which occur during acceleration and highway-type driving. The second support 24 is designed to provide additional NOx conversion. Typically, the second support precious metal loadings are generally much lower, for example, 10 g/ft3 Pd and 2 g/ft3 Rh.
With such a typical catalyst support configuration and composition, we have determined that during vehicle acceleration, the catalyst on the first support generates N2O due to the incomplete reduction of NOx compounds by the three way catalyst and the presence of higher levels of carbon monoxide which inhibit the activity of the three-way catalyst. The catalyst on the second support is not effective to significantly reduce the N2O content of the exhaust.
To address the shortcomings of current catalytic exhaust systems, embodiments of the present invention utilize a zoned catalyst system that includes a first zone that comprises rhodium or a rhodium-enriched catalyst and a second zone, positioned downstream from the first zone, that comprises palladium or a palladium-enriched catalyst. The catalyst zones may be located on separate catalyst support structures positioned in sequence. Alternatively, the catalyst zones may be positioned sequentially on a single catalyst support.
The catalyst support or supports are preferably positioned close to the exhaust gas manifold of the engine to receive the hot exhaust gases therefrom. This configuration is termed in the art a “close-coupled” catalyst and is designed to provide faster catalyst light off (e.g., the catalyst is heated and reaches its light off temperature more quickly) after a cold start of the vehicle. Optionally, the second catalytic zone may include a nickel-copper catalyst. Alternatively, the nickel-copper catalyst may be positioned in a third catalytic zone located downstream from the second catalytic zone.
As shown in
Generally, the first catalyst zone comprises from about 5 to about 35% of the length of the support. In a preferred embodiment, the first catalyst zone comprises from about 8 to about 30% of the length. If the two catalyst zones are positioned on separate supports, the relative lengths will be in the same ratio. The catalyst in the first zone comprises from about 50 to about 100 wt % rhodium, with the remainder comprising palladium and/or platinum in any weight ratio. Thus, the amount of palladium in the first catalytic zone may vary from 0 to about 50 wt. % and the amount of platinum in the first catalytic zone may vary from 0 to about 50 wt. %. The catalyst loading for the first zone is between about 0.5 and about 300 gm/ft3.
The catalyst in the second zone comprises from about 50 to about 100 wt % palladium, with the remainder comprising platinum and/or rhodium in any weight ratio. Thus, the amount of rhodium in the second catalytic zone may vary from 0 to about 50 wt. % and the amount of platinum in the second catalytic zone may vary from 0 to about 50 wt. %. The catalyst loading in the second zone comprises from about 0.5 to about 300 gm/ft3.
By locating the rhodium or rhodium-enriched catalyst so that engine exhaust gases encounter it first, NOx conversion is enhanced while N2O formation is minimized. While not wishing to be bound by any particular theory, vehicle acceleration events are characterized by higher exhaust gas flow rates, with the exhaust gases containing relatively greater amounts of NOx and CO. Under lower temperature and CO rich reaction conditions, rhodium has a lower light off temperature than palladium, with 50% NOx reduction occurring at about 300° C. for rhodium versus about 400° C. for palladium.
Rhodium has the additional advantage in that it is a good water gas shift reaction catalyst, converting the CO present in the exhaust gas to CO2 and H2. The catalytic activity of rhodium is not adversely affected by CO, more CO is converted, and less CO is present in the downstream exhaust gas which avoids adversely affecting the catalytic activity of the palladium catalyst zone. Further, the H2 produced in the rhodium catalytic zone is utilized by the downstream palladium or palladium-enriched catalyst to enhance the conversion of any remaining N2O in the exhaust stream.
In another embodiment, the second catalytic zone 60 includes a nickel-copper catalyst booster that enhances the conversion unburned hydrocarbons, carbon monoxide, NOx, N2O, and NH3. The catalyst loading for the nickel-copper catalyst is from about 0.5 to about 2000 gm/ft3 total nickel and copper. The weight ratio of nickel to copper may vary widely from about 1:99 to about 99:1. Preferably, the nickel to copper weight ratio (Ni/Cu) is >1.
Alternatively, the nickel-copper catalyst may be positioned in a third catalyst zone downstream from the second zone. In one simplified three-zone embodiment illustrated in
In order that embodiments of the invention may be better understood, reference is made to the following examples which are intended to illustrate the various embodiments of the invention and are not intended to limit the scope thereof.
Laboratory tests were run to simulate vehicle acceleration conditions for an exhaust having rich CO levels, i.e., levels of CO greater than stoichiometric for the reaction 2NO+CO→N2+CO2. Two different catalysts were compared. The first catalyst comprised rhodium at a level of 26 g/ft3. The second catalyst comprised Pd at a level of 26 g/ft3. In each instance, the catalysts were washcoated onto the walls of a ceria/zirconia honeycomb support 1 inch in diameter and 0.5 inches in length having 400 cells per square inch and a 0.004 inch wall thickness. The evaluation parameters were simulated exhaust gas at a space velocity of 60,000/hr and a reactor total flow rate of 6.44 liters/min. Both catalysts were aged for 16 hrs. at 900° C. under hydrothermal conditions.
Three different levels of CO were used, a stoichiometric level of CO (2000 ppm of both NO and CO, a Rich Level 1 of CO (2000 ppm NO and 3000 ppm CO), and a Rich Level 2 of CO (2000 ppm NO and 5000 ppm CO). The tests compared NOx conversion, N2O formation, CO conversion, and NH3 formation using the two different catalysts at increasing gas inlet temperatures. As shown in
The results of the testing show that the Rh catalyst converted 50% of NOx compounds at lower temperatures (220° C. versus 270° C. for Pd), and was not affected by rich levels of CO, whereas the Pd catalyst was inhibited by 130° C. (compare
It is noted that terms like “preferably,” “commonly,” and “typically” are not utilized herein to limit the scope of the claimed invention or to imply that certain features are critical, essential, or even important to the structure or function of the claimed invention. Rather, these terms are merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the present invention.
Unless the meaning is clearly to the contrary, all ranges set forth herein are deemed to be inclusive of all values within the recited range as well as the endpoints.
For the purposes of describing and defining the present invention it is noted that the term “substantially” is utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “substantially” is also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
Having described the invention in detail and by reference to specific embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. More specifically, although some aspects of the present invention are identified herein as preferred or particularly advantageous, it is contemplated that the present invention is not necessarily limited to these preferred aspects of the invention.
