Patent Grant
9579604
Field of the Disclosure
The present disclosure relates generally to catalyst materials for reducing engine exhaust emissions, and more particularly, to improved close-coupled catalysts for three-way catalyst (TWC) applications.
Background Information
Current automotive catalysts largely depend on platinum group metals (PGM) (e.g., Platinum, Palladium, and Rhodium) in order to convert vehicle emissions to less noxious substances. However, the supply of said metals is limited even as automobile production increases as a larger portion of the world population adopts motorized vehicles for transport. Additionally, environmental concerns have led to ever more stringent NOX, hydrocarbon (HC), and particulate emission regulations being adopted in countries throughout the world. As such, there is a continuing need for catalysts able to provide better catalytic performance while maintaining reasonable use of PGM. One way of improving the light-off performance of a TWC close-coupled catalyst is to reduce its heat capacity per unit which can be accomplished by reducing the mass of the substrate by decreasing its wall thickness or increasing its porosity. Unfortunately, employing thinner or more porous walls can create a problematic reduction in the mechanical strength of the substrate.
Accordingly, there is a continuing need to provide TWC close-coupled catalysts capable of providing sufficient conversion so that stringent HC, NOX and particulates emission limits can be accomplished cost-effectively.
The present disclosure describes the effects that result from different three-way catalyst (TWC) material compositions including light-weighted ceramic substrates in which a single coating of Iron (Fe)-activated Rhodium (Rh) is applied to the substrates to enable performance synergies with low loadings of platinum group metals (PGM) material compositions within conventional TWC systems. Further, the present disclosure describes improved light-off catalytic behavior and steady-state conversion efficiency for cumulative emissions, specifically nitrogen oxide (NOX), for close-coupled catalysts (CCCs) employing Fe-activated Rh, in comparison with the catalytic behavior of conventional CCCs including standard ceramic substrates in which coatings of PGM employ heavy loadings of material compositions that are applied onto the standard ceramic substrate.
In some embodiments, samples of a CCC, herein referred as CCC Type 1A catalyst samples, are produced including a suitable light-weighted ceramic substrate in which a thin coating of Fe-activated Rh is applied onto the suitable light-weighted ceramic substrate, for a total loading of about 90 g/L. In these embodiments, the produced samples of CCC Type 1A catalyst sample comprise deposition layers including Rh and iron (Fe) supported on an oxygen storage material (OSM) composition including Ceria (Ce), Zirconia (Zr), Neodymia (Nd), Praseodymia (Pr), Yttria (Y), or combinations thereof, amongst others. Further to these embodiments, Rh and Fe loadings can vary within a range from about 1 g/ft3 to about 20 g/ft3 for Rh and about 1 wt % to about 20 wt % for Fe. Still further to these embodiments, the produced samples of CCC Type 1A catalyst sample include Rh loadings of about 3 g/ft3 and Fe loadings of about 7.37 wt %. Examples of OSM include Ceria-Zirconia mixed oxide with fluorite phases, other mixed oxides including Ceria, and other Ceria-containing materials including additional oxides. In these embodiments, samples of CCC Type 1A includes a thin coating of Fe activated Rh employing a loading of about 3 g/ft3. In some embodiments, the aforementioned CCC samples produced are aged at about 1000° C. for about 20 hours under dyno-aging using the multi-mode aging cycle on a bench reactor.
In other embodiments, samples of a CCC, herein referred as CCC Type 1C catalyst samples, are produced including a suitable light-weighted ceramic substrate in which a thin coating of Fe activated Rh is applied onto the suitable light-weighted ceramic substrate, for a total loading of about 90 g/L. In these embodiments, the produced samples of CCC Type 1C comprise deposition layers including Rh and iron (Fe) supported on an oxygen storage material (OSM) composition including Ceria, Zirconia, Neodymia, Praseodymia, Yttria, or combinations thereof, amongst others. Further to these embodiments, Rh and Fe loadings can vary within a range from about 1 g/ft3 to about 20 g/ft3 for Rh and from about 1 wt % to about 20 wt % for Fe. Still further to these embodiments, the produced samples of CCC Type 1C include Rh loadings of about 0.38wt % and Fe loadings of about 7.37 wt %. Examples of OSM include Ce—Zr mixed oxide with fluorite phases, other mixed oxides including Ce, and other Ce-containing materials including additional oxides. In these embodiments, samples of CCC Type 1C includes a thin coating of Fe-activated Rh employing a loading of about 9.8 g/ft3
In some embodiments, samples of a CCC, herein referred as CCC Type 1B catalyst samples, are produced including a thin coating of non-activated (standard) Rh deposited onto a suitable light-weighted ceramic substrate. In these embodiments, Rh loading of about 9.8 g/ft3 is employed to produce the catalyst samples.
In other embodiments, samples of a standard CCC, herein referred as CCC Type 2 catalyst samples, are produced including a ceramic substrate in which a coating of PGM based coating is deposited onto the ceramic substrate. In these embodiments, a multi-layer coating of Palladium (Pd)/Rh, with total load of about 300 g/L is deposited onto the ceramic substrate. In some embodiments, the aforementioned CCC samples produced are aged at about 950° C. for about 50 hours under dyno-aging using the multi-mode aging cycle.
In some embodiments, NOX conversion efficiencies for CCC Type 1A and CCC Type 1B catalyst samples are compared after an isothermal light-off test at a temperature of 350° C. and space velocities within a range from about 20,000 hr-1 to about 180,000 hr-1, according to an embodiment.
In other embodiments, CCC sample testing for CCC Type 1B, CCC Type 1C, CCC Type 2 catalyst samples is conducted using a car engine with ports located on the exhaust to measure the emissions, according to the testing protocol in the Environmental Protection Agency Federal Test Procedure 75 (FTP-75), using a vehicle speed profile established for the dyno drive cycle. In these embodiments, the results measured during FTP-75 test are compared to verify improved performance levels of the CCC Type 1C catalyst sample versus the CCC Type 1B catalyst sample and the standard CCC Type 2 catalyst sample. Further to these embodiments, the effect of the single coating of Fe-activated Rh on NOx conversion is analyzed and determined by comparing the cumulative grams of NOX emissions, measured downstream at the tail pipe, associated with the CCC Type 1C, CCC Type 1B, and the standard CCC Type 2 catalyst samples.
The CCC system includes a thin coating of Fe-activated Rh employing a loading of about 3 g/ft3 to about 9.8 g/ft3 and further employing loadings of Fe with Ce—Zr OSM and outperforms the other catalysts when their respective light-off and performance are compared. These results enable potential benefits, such as, for example reduced costs, improved NOx conversion, etc. when implemented within a plurality of TWC system applications.
Numerous other aspects, features and benefits of the present disclosure may be made apparent from the following detailed description taken together with the drawing figures.
The present disclosure can be better understood by referring to the following figures. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the disclosure. In the figures, reference numerals designate corresponding parts throughout the different views.
The present disclosure is described herein in detail with reference to embodiments illustrated in the drawings, which form a part hereof. Other embodiments may be used and/or other modifications may be made without departing from the scope or spirit of the present disclosure. The illustrative embodiments described in the detailed description are not meant to be limiting of the subject matter presented.
Definitions
As used here, the following terms have the following definitions:
“Air to fuel ratio, or A/F ratio, or AFR” refers to the mass ratio of air to fuel present in a combustion process.
“Catalyst” refers to one or more materials that may be of use in the conversion of one or more other materials.
“Catalytic converter” refers to a vehicle emissions control device that converts toxic pollutants in exhaust gas to less toxic pollutants by catalyzing a redox reaction (oxidation or reduction).
“Catalyst system” refers to any system including a catalyst, such as, a PGM catalyst or a ZPGM catalyst of at least two layers comprising a substrate, a washcoat and/or an overcoat.
“Close-coupled catalyst” refers to a catalyst located in close proximity to the exhaust manifold of the engine and reduces cold-engine emissions.
“Conversion” refers to the chemical alteration of at least one material into one or more other materials.
“Conversion efficiency” refers to the percentage of emissions passing through the catalyst that are converted to their target compounds.
“Federal Test Procedure 75 or FTP-75” refers to a city driving cycle during which a series of tests defined by the US Environmental Protection Agency (EPA) are conducted to measure tailpipe emissions and fuel economy of passenger cars.
“Lean condition” refers to an exhaust gas condition with an R-value less than 1 and having excess oxidants.
“Light off” refers to the time elapsed from an engine cold start to the point of 50 percent pollutant conversion.
“Oxygen storage material (OSM)” refers to a material that absorbs oxygen from oxygen rich gas flows and further able to release oxygen into oxygen deficient gas flows.
“Platinum group metals (PGM)” refers to platinum, palladium, ruthenium, iridium, osmium, and rhodium.
“R-value” refers to the value obtained by dividing the total reducing potential of the gas mixture (in moles of Oxygen) by the total oxidizing potential of the gas mixture (in moles of Oxygen).
“Rich condition” refers to an exhaust gas condition with an R-value greater than 1 and having excess reductants.
“Stoichiometric condition” refers to an exhaust gas condition with an R-value equal to 1.
“Substrate” refers to any material of any shape or configuration that yields a sufficient surface for depositing a washcoat layer and/or an overcoat layer.
“Support oxide” refers to porous solid oxides, typically mixed metal oxides, which are used to provide a high surface area which aids in oxygen distribution and exposure of catalysts to reactants such as NOx, CO, and hydrocarbons.
“Three-Way Catalyst (TWC)” refers to a catalyst able to perform the three simultaneous tasks of reduction of nitrogen oxides to nitrogen and oxygen, oxidation of carbon monoxide to carbon dioxide, and oxidation of unburnt hydrocarbons to carbon dioxide and water.
Description of the Disclosure
The present disclosure is directed to three-way catalyst (TWC) material compositions including light-weighted ceramic substrates in which a single, thin layer coating of Fe-activated Rhodium (Rh) is applied to the substrates to enable performance synergies with lower loadings of platinum group metals (PGM) material compositions within conventional TWC systems. Further, the present disclosure describes improved light-off catalytic behavior and steady-state conversion efficiency for cumulative emissions, specifically nitrogen oxide (NOX), for close-coupled catalysts (CCCs) including Fe-activated Rh. The improved light-off catalytic behavior and steady-state conversion efficiency for cumulative emissions are measured in comparison with the light-off catalytic behavior of conventional CCCs including coatings of PGM employing heavy loadings of material compositions that are applied onto ceramic substrates.
As used herein, and as an illustrative example, loading of a washcoat is the mass of washcoat deposited on a substrate divided by a catalyst system volume. Loading of an overcoat or a component of the washcoat or the overcoat has a corresponding meaning about the weight of that layer or component divided by the volume of the catalyst system. As shown in Example 3.1 of R. E. Hayes and Stan T. Kolaczkowski, Introduction to Catalytic Combustion, 310-313(1997), a washcoat loading divided by the fraction of the volume of a reactor that is taken up by the washcoat is equal to the density of the washcoat, confirming the usage. In more detail, the washcoat area divided by the total area of a reactor produces a fraction equivalent to the volume of the washcoat divided by the volume of the reactor (in the example, 0.112). Dividing the loading of the washcoat (in the example, 170 g/L), by the aforementioned fraction, equals the weight of the washcoat divided by the volume of the washcoat, or the washcoat density. Consequently, the washcoat loading, (in the example, 170 g/L), equals the mass of the washcoat divided by the volume of the reactor. Accordingly, washcoat loading is the mass of washcoat deposited on the substrate divided by the catalyst system volume. As recognized by persons of ordinary skill in the art, expressing loading as a concentration refers to the mass of the loaded component or layer divided by the volume of a catalyst system.
Production of Close-Coupled Catalyst Samples
The present disclosure includes TWC systems employing CCC samples to determine the effect of using Fe-activated Rh coatings deposited onto light-weight ceramic substrates
In some embodiments, a CCC sample, herein referred to as CCC Type 1A catalyst sample, including a Fe-activated Rh coating that is deposited onto a light-weight substrate is produced. In these embodiments, the substrate employed has dimensions of about 4.66″ diameter, 3.58″ length, 600 cells per square inch (CPSI), and 2.75 mil wall thickness. The deposition layer includes suitable loadings of Fe-activated Rh and suitable loadings of Iron (Fe), and a suitable oxygen storage material (OSM) composition, such as, for example Ceria (Ce), Zirconia (Zr), Neodymia (Nd), Praseodymia (Pr), Yttria (Y) mixed oxide, amongst others. Further to these embodiments, the deposition layer includes Fe-activated Rh loadings with a combined weight-percentage ranging from about 1 wt % to about 20 wt % of Fe. Still further to these embodiments, the catalyst sample of CCC Type 1A includes an Fe-activated Rh loading of about 3 g/ft3 Rh, an Fe loading of about 7.37 wt %, and the OSM for the remaining amount. In these embodiments, the OSM includes a Ceria-Zirconia mixed oxide with fluorite phases. Further to these embodiments, other OSMs are used including Ceria, or other Ceria-containing materials that may include additional oxides. In these embodiments, a total loading of about 90 g/L (approximately, 2548 g/ft3) is achieved with Fe-activated Rh loading of about 3 g/ft3, Fe loading of about 215 g/ft3, and OSM for the remaining amount.
In other embodiments, a CCC sample, herein referred to as CCC Type 1C catalyst sample, including a Fe-activated Rh coating that is deposited onto a light-weight substrate is produced. In these embodiments, the substrate has similar dimension as the substrate used for CCC Type 1A, and the deposition layer includes suitable loadings of Fe-activated Rh and suitable loadings of Iron (Fe), and a suitable oxygen storage material (OSM) composition, such as, for example Ceria (Ce)-Zirconia (Zr)-Neodymia (Nd)-Praseodymia (Pr)-Yttria (Y) mixed oxide, amongst others. Further to these embodiments, the deposition layer includes Fe-activated Rh loadings with a combined weight-percentage ranging from about 1 wt % to about 20 wt % of Fe. Still further to these embodiments, the catalyst sample of CCC Type 1C includes a Fe-activated Rh loading of about 0.38 wt %, an Fe loading of about 7.37 wt %, and the OSM for the remaining amount. In these embodiments, the OSM includes a Ceria-Zirconia mixed oxide with fluorite phases. Further to these embodiments, other OSMs are used including Ceria, or other Ceria-containing materials that may include additional oxides. In these embodiments, a total loading of about 90 g/L (approximately, 2548 g/3) is achieved with Fe-activated Rh loading of about 9.8 g/ft3, Fe loading of about 215 g/ft3, and OSM for the remaining amount.
In some embodiments, a CCC samples herein referred as CCC Type 1B catalyst sample, is produced. In these embodiments, the substrate has similar dimension as the substrate used for CCC Type 1A, and the CCC Type 1B catalyst sample includes a standard Rh coating deposited onto a suitable light-weight ceramic substrate. Further to these embodiments, a standard Rh loading of about 9.8 g/ft3 is employed to produce the Type 1B catalyst samples with a total loading of about 90 g/L. In these embodiments, the CCC Type 1B catalyst sample includes substantially similar OSM as CCC Type 1A and CCC Type 1C catalyst samples.
In other embodiments, a sample of a conventional CCC, herein referred as a CCC Type 2 catalyst sample, is produced. In these embodiments, the CCC Type 2 catalyst sample includes a ceramic substrate on which a coating of platinum group metals (PGM) loadings is deposited. Further to these embodiments, a multi-layer coating of Palladium (Pd)/Rh, with a total loading of about 300 g/L (approximately, 8495 g/ft3), is deposited onto the ceramic substrate. In these embodiments, the s coating of Pd/Rh includes loading of about 50 g/ft3 Pd and about 9.8 g/ft3 Rh. Further to these embodiments, CCC Type 2 catalyst samples include OSM and Alumina for the remaining amount.
Aging of Close-Coupled Catalyst Samples
In some embodiments, as described in
In other embodiments, as described in
Test Methodology
In some embodiments, testing of the CCC samples is conducted using a car engine that includes ports added to the exhaust of the car engine to measure engine emissions according to the testing protocol requirements within the Environmental Protection Agency Federal Test Procedure75 (FTP-75), using a vehicle speed profile established for the dyno drive cycle. In these embodiments, a single roll chassis dynamometer is employed to conduct the FTP-75 tests. Further to these embodiments, the engine emissions that are continuously measured during the FTP-75 tests are compared to determine/verify improved performance levels of CCC Type 1C, CCC Type 1B, and conventional CCC Type 2 catalyst samples. In these embodiments, the effect of the single, thin coating of Fe-activated Rh is analyzed/determined by comparing the cumulative grams of NOX conversion that is measured downstream at the tail pipe for CCC Type 1C, CCC Type 1B, and conventional CCC Type 2 catalyst samples.
Performance of Fe-Activated Rh Thin Coatings
In some embodiments, conversion curve 102 illustrates NOX conversion associated with a CCC Type 1A catalyst sample. In these embodiments, conversion curve 104 illustrates NOX conversion associated with a CCC Type 1B catalyst sample. Further to these embodiments, the catalytic activity of the CCC Type 1A and CCC Type 1B catalyst samples in
In these embodiments, for increasing space velocities within a range from about 100,000 hr−1 to about 180,000 hr−1, the CCC Type 1A catalyst sample maintains a significantly high NOX conversion percentage rate within a slightly decreasing range from about 99% to 95%. Further to these embodiments, for increasing space velocities within a range from about 100,000 hr−1 to about 180,000 hr−1, the CCC Type 1B catalyst sample continues to exhibit a decreasing NOX conversion percentage rate within a range from about 75% to about 67%. In
In some embodiments, accumulation curve 202 illustrates total NOX accumulation associated with CCC Type 1C catalyst samples. In these embodiments, accumulation curve 204 illustrates total NOx accumulation associated with CCC Type 1B catalyst samples. Further to these embodiments, vehicle speed curve 206 illustrates the vehicle speed profile used during the implementation of the FTP-75 test protocol for testing the aforementioned CCC samples.
In some embodiments, the results measured during the FTP-75 test protocol are compared and verify that thin coatings including low loadings of Fe-activated Rh provide improved NOx conversion performance levels versus standard Rh applications. In these embodiments, the effects of the thin coatings including low loadings of Fe-activated Rh on NOX accumulation are analyzed during all cycles of the FTP-75 test protocol to verify improvements in NOx conversion efficiency. Further to these embodiments, the effects of the thin coatings including low loadings of Fe-activated Rh on NOX conversion are verified by comparing the accumulated grams of NOX for CCC Type 1C catalyst samples with the accumulated grams of NOX for CCC Type 1B catalyst samples, measured downstream at the tail pipe.
In these embodiments, it is observed in
In some embodiments, accumulation curve 202 illustrates NOX accumulation associated with CCC Type 1C catalyst samples. In these embodiments, accumulation curve 204 illustrates NOX accumulation associated with CCC Type 1B catalyst samples. Further to these embodiments, accumulation curve 302 illustrates NOX accumulation associated with CCC Type 2 catalyst samples. Still further to these embodiments, vehicle speed curve 206 illustrates the vehicle speed profile used during the implementation of the FTP-75 test protocol for testing the aforementioned CCC samples. In
In some embodiments, the results measured during the FTP-75 test protocol are compared and verify that thin coatings including low loadings of Fe-activated Rh provide improved NOx conversion performance levels when compared to standard Rh applications as well as a standard catalyst samples employing multi-layer coatings of Pd/Rh. In these embodiments, the effects of the thin coatings including low loadings of Fe-activated Rh on NOX accumulation are analyzed during all cycles of the FTP-75 test protocol to verify improvements in conversion efficiency. Further to these embodiments, the effects of the thin coatings including low loadings of Fe-activated Rh on NOX conversion are verified by comparing the accumulated grams of NOX for the CCC Type 1C catalyst samples with the accumulated grams of NOX for CCC Type 1B catalyst samples and with the accumulated grams of NOX for CCC Type 2 catalyst samples, measured downstream at the tail pipe.
In these embodiments, it is observed in
In other embodiments and in the third part (Bag 3) of the FTP-75 test procedure (not shown), the CCC Type 2 catalyst samples exhibit improved Bag 3 performance. However, even with extra Pd the CCC Type 2 catalyst samples exhibit a lower light-off performance than the CCC Type 1B catalyst samples as CCC Type 2 catalyst samples have about three times the coating mass of CCC Type 1B catalyst samples. In these embodiments, the accumulation of NOx emissions during the FTP-75 test procedure, illustrated in
This application claims the benefit of U.S. application Ser. No. 62/008,674, filed Jun. 6, 2014, and U.S. application Ser. No. 62/163,231, filed May 18, 2015, each of which are hereby incorporated by reference in their entireties.
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