Synergized PGM Catalyst Systems Including Palladium for TWC Application

Info

Publication number: 20150238940
Type: Application
Filed: Feb 24, 2014
Publication Date: Aug 27, 2015
Applicant: CLEAN DIESEL TECHNOLOGIES INC. (CDTI) (Ventura, CA)
Inventors: Zahra Nazarpoor (Camarillo, CA), Stephen J. Golden (Santa Barbara, CA)
Application Number: 14/187,580

Abstract

Synergized Platinum Group Metals (SPGM) catalyst system for TWC application is disclosed. Disclosed SPGM catalyst system may include a washcoat with a Cu—Mn stoichiometric spinel structure and an overcoat that includes PGM, such as palladium (Pd) supported on carrier material oxides, such as alumina. SPGM catalyst system shows significant improvement in nitrogen oxide reduction performance under lean operating conditions, which allows a reduced consumption of fuel. Additionally, disclosed SPGM catalyst system also exhibits enhanced catalytic activity for carbon monoxide conversion. Furthermore, disclosed SPGM catalyst systems are found to have enhanced catalytic activity for fresh and aged conditions compared to PGM catalyst system, showing that there is a synergistic effect between PGM catalyst and Cu—Mn spinel within the disclosed SPGM catalyst system which help in thermal stability of disclosed SPGM catalyst.

Description

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to U.S. patent application Ser. No. 14/090,861, filed Nov. 26, 2013, entitled System and Methods for Using Synergized PGM as a Three-Way Catalyst.

BACKGROUND

1. Technical Field

The present disclosure relates generally to PGM catalyst systems, and, more particularly, to synergized PGM catalyst systems with lean and rich performance improvement.

2. Background Information

Catalysts in catalytic converters have been used to decrease the pollution caused by exhaust from various sources, such as automobiles, utility plants, processing and manufacturing plants, airplanes, trains, all-terrain vehicles, boats, mining equipment, and other engine-equipped machines. Important pollutants in the exhaust gas of internal combustion engines may include carbon monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides (NOx), and particulate matter (PM). Several oxidation and reduction reactions take place in the catalytic converter, which is capable of removing the major pollutants HC, CO and NO_xsimultaneously, therefore, it is called a three-way catalyst.

Catalytic converters are generally fabricated using at least some platinum group metals (PGM). With the ever stricter standards for acceptable emissions, the demand on PGM continues to increase due to their efficiency in removing pollutants from exhaust. However, this demand, along with other demands for PGM, places a strain on the supply of PGM, which in turn drives up the cost of PGM and therefore catalysts and catalytic converters. Additionally, engines associated with TWC using PGM operate at or near stoichiometric conditions.

Catalytic materials used in TWC applications have also changed, and the new materials have to be thermally stable under the fluctuating exhaust gas conditions. The attainment of the requirements regarding the techniques to monitor the degree of the catalyst's deterioration/deactivation demands highly active and thermally stable catalysts in which fewer constituents may be provided to reduce manufacturing costs, offer additional economic alternatives, and maintain high performance materials with optimal thermal stability and enhanced performance due to its facile nature of the redox function of the used chemical components.

For the foregoing reasons, there is a need for combined catalyst systems that include low amounts of PGM catalysts, which may have facile nature of the redox function of the used chemical components, and which may exhibit optimal synergistic behavior yielding enhanced activity and performance under both lean condition and rich condition.

SUMMARY

The present disclosure provides Synergized Platinum Group Metals (SPGM) catalyst systems which may exhibit high catalytic activity, under both lean condition and rich condition, and thus enhanced NO and CO conversion compared to PGM catalyst systems.

According to an embodiment, SPGM catalyst system may include at least a substrate, a washcoat, and an overcoat, where substrate may include a ceramic material, washcoat may include a Cu—Mn spinel structure supported on doped ZrO₂, and overcoat may include PGM catalyst such as Palladium (Pd) supported on carrier material oxides, such as alumina.

In order to compare performance and determine synergism of Cu—Mn spinel with Pd catalyst, a PGM catalyst system without Cu—Mn spinel structure may be prepared, where PGM catalyst system may include a ceramic material, a washcoat that may include doped ZrO₂, and an overcoat may include PGM catalyst such as Pd supported on carrier material oxides, such as alumina.

Additionally, samples of disclosed SPGM catalyst system and samples of PGM catalyst system without Cu—Mn spinel structure that include different loadings of Pd, such as 1 gift³and 6 gift³, may be prepared to determine effect of PGM loading on synergetic property.

Disclosed SPGM catalyst system may be prepared using suitable known in the art synthesis method, such as co-milling process, and co-precipitation process, among others.

According to one aspect of the present disclosure, fresh and aged samples of disclosed SPGM catalyst system and of PGM catalyst system may be prepared, including different amounts of Pd loadings, in order to compare catalytic activity of disclosed SPGM catalyst system (including Cu—Mn spinel) with PGM catalyst systems (without Cu—Mn spinel).

Catalytic activity in fresh, hydrothermally aged (900° C. during about 4 hours), and fuel cut aged (800° C. during about 20 hours) samples of disclosed SPGM catalyst system and of PGM catalyst system may be determined by performing isothermal steady state sweep tests under stoichiometric conditions, in a range of rich to lean conditions, and compared with results for disclosed SPGM catalyst system with PGM catalyst systems.

SPGM catalyst system of the present disclosure may show surprisingly significant improvement in nitrogen oxide conversion under stoichiometric operating conditions and especially under lean operating conditions which may allow reduced consumption of fuel. It has been shown that the enhanced catalytic activity is produced by the synergistic effect of Cu—Mn spinel on Pd (PGM catalyst). Furthermore, disclosed SPGM catalyst system that includes a Cu—Mn spinel may enable the use of a catalyst converter that includes low amounts of PGM.

Furthermore, isothermal sweep test results, performed on both disclosed SPGM catalyst system and PGM catalyst system depicts that disclosed SPGM catalysts systems may result in enhanced activity for both NO conversion and CO conversions.

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.

BRIEF DESCRIPTION OF THE DRAWINGS

Non-limiting 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 the background art, the figures represent aspects of the disclosure.

FIG. 1 shows a SPGM catalyst system configuration with Cu—Mn spinel referred as SPGM catalyst system Type 1, according to an embodiment.

FIG. 2 illustrates a PGM catalyst system configuration with no Cu—Mn spinel referred as catalyst system Type 2, according to an embodiment.

FIG. 3 depicts NOx conversion comparison for fresh samples of SPGM catalyst systems Type 1, and PGM catalyst system Type 2, under isothermal steady state sweep condition, at inlet temperature of about 450° C. and space velocity (SV) of about 40,000 h⁻¹, according to an embodiment. FIG. 3A depicts PGM loading of 1 g/ft³and FIG. 3B depicts PGM loading of 6 g/ft³.

FIG. 4 depicts NOx conversion comparison for hydrothermally aged samples (at 900° C. during about 4 hours) of SPGM catalyst systems Type 1 and PGM catalyst system Type 2, under isothermal steady state sweep condition, at inlet temperature of about 450° C., and SV of about 40,000 h⁻¹, according to an embodiment. FIG. 4A depicts PGM loading of 1 gift' and FIG. 4B depicts PGM loading of 6 g/ft³.

FIG. 5 depicts NOx conversion comparison for fuel cut aged samples (at 800° C. during about 20 hours) of SPGM catalyst systems Type 1 and PGM catalyst system Type 2, under isothermal steady state sweep condition, at inlet temperature of about 450° C., and SV of about 40,000 h⁻¹, according to an embodiment. FIG. 5A depicts PGM loading of 1 gift' and FIG. 5B depicts PGM loading of 6 g/ft³.

FIG. 6 depicts CO conversion comparison for fresh sample and hydrothermally aged samples (at 900° C. during about 4 hours) of SPGM catalyst systems Type 1 and PGM catalyst system Type 2 with PGM loading of 1 gift' under isothermal steady state sweep condition, at inlet temperature of about 450° C., and SV of about 40,000 h⁴, according to an embodiment. FIG. 6A depicts fresh sample and FIG. 6B depicts hydrothermally aged samples.

FIG. 7 depicts CO conversion comparison for fuel cut aged samples (at 800° C. during about 20 hours) of SPGM catalyst systems Type 1 and PGM catalyst system Type 2, under isothermal steady state sweep condition, at inlet temperature of about 450° C., and SV of about 40,000 h⁻¹, according to an embodiment. FIG. 7A depicts PGM loading of 1 gift' and FIG. 7B depicts PGM loading of 6 g/ft³.

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 may have the following definitions:

“Catalyst system” refers to a system of at least two layers including at least one substrate, a washcoat, and/or an overcoat.

“Substrate” refers to any material of any shape or configuration that yields a sufficient surface area for depositing a washcoat and/or overcoat.

“Washcoat” refers to at least one coating including at least one oxide solid that may be deposited on a substrate.

“Overcoat” refers to at least one coating that may be deposited on at least one washcoat layer.

“Catalyst” refers to one or more materials that may be of use in the conversion of one or more other materials.

“Milling” refers to the operation of breaking a solid material into a desired grain or particle size.

“Co-precipitation” refers to the carrying down by a precipitate of substances normally soluble under the conditions employed.

“Calcination” refers to a thermal treatment process applied to solid materials, in presence of air, to bring about a thermal decomposition, phase transition, or removal of a volatile fraction at temperatures below the melting point of the solid materials.

“Platinum group metals (PGM)” refers to platinum, palladium, ruthenium, iridium, osmium, and rhodium.

“Synergized platinum group metal (SPGM) catalyst” refers to a PGM catalyst system which is synergized by a non-PGM group metal compound under different configuration.

“Zero Platinum group metals (ZPGM)” refers to catalyst system that is free of PGM.

“Treating,” “treated,” or “treatment” refers to drying, firing, heating, evaporating, calcining, or mixtures thereof.

“Three-Way Catalyst” refers to a catalyst that may achieve three simultaneous tasks: reduce nitrogen oxides to nitrogen and oxygen, oxidize carbon monoxide to carbon dioxide, and oxidize unburnt hydrocarbons to carbon dioxide and water.

“R-Value” refers to the number obtained by dividing the reducing potential by the oxidizing potential.

“Lean condition” refers to exhaust gas condition with an R-value below 1.

“Rich condition” refers to exhaust gas condition with an R value above 1.

“Stoichiometric condition” refers to the condition when the oxygen of the combustion gas or air added equals the amount for completely combusting the fuel.

“Conversion” refers to the chemical alteration of at least one material into one or more other materials.

“Spinel” refers to any of various mineral oxides of magnesium, iron, zinc, or manganese in combination with aluminum, chromium, copper or iron with AB₂O₄structure.

DESCRIPTION OF THE DRAWINGS

The present disclosure may generally provide a synergized PGM (SPGM) catalyst system which may have enhanced catalytic performance of PGM catalyst under both lean condition and rich condition, by incorporating more active components into phase materials possessing three-way catalyst (TWC) properties.

Embodiments of the present disclosure provide catalyst performance comparison of disclosed SPGM catalyst system and a PGM catalyst system that may include different Palladium (Pd) loadings within the overcoat of disclosed SPGM catalyst systems, and PGM catalyst system.

According to embodiments in the present disclosure, SPGM catalyst systems may be configured with a washcoat including stoichiometric Cu—Mn spinel with doped ZrO2 support oxide such as Niobium-Zirconia, an overcoat including a PGM catalyst, such as Pd with alumina-based support, and suitable ceramic substrate, here referred as SPGM catalyst system Type 1. According to embodiments in the present disclosure, PGM catalyst systems may be configured with washcoat layer including doped ZrO2 support oxide such as Niobium-Zirconia, an overcoat including PGM catalyst, such as Pd with alumina-based support, and suitable ceramic substrate, here referred as PGM catalyst system Type 2.

Catalyst System Configuration

FIG. 1 shows a SPGM catalyst system configuration referred as SPGM catalyst system Type 1 100, according to an embodiment.

As shown in FIG. 1, SPGM catalyst system Type 1 100 may include at least a substrate 102, a washcoat 104, and an overcoat 106, where washcoat 104 may include a Cu—Mn spinel structure, Cu_1.0Mn_2.0O₄, supported on doped ZrO2 and overcoat 106 may include PGM catalyst, such as Palladium (Pd) supported on carrier material oxides, such as alumina.

In an embodiment, substrate 102 materials for SPGM catalyst system Type 1 100 may include a refractive material, a ceramic material, a honeycomb structure, a metallic material, a ceramic foam, a metallic foam, a reticulated foam, or suitable combinations, where substrate 102 may have a plurality of channels with suitable porosity. Porosity may vary according to the particular properties of substrate 102 materials. Additionally, the number of channels may vary depending upon substrate 102 used as is known in the art. The type and shape of a suitable substrate 102 would be apparent to one of ordinary skill in the art. According to the present disclosure, preferred substrate 102 materials may be ceramic material.

According to an embodiment, washcoat 104 for SPGM catalyst system Type 1 100 may include a Cu—Mn stoichiometric spinel, Cu_1.0Mn_2.0O₄, as non PGM metal catalyst. Additionally, washcoat 104 may include support oxide such as zirconium oxide, doped zirconia. According to the present disclosure, suitable material for disclosed washcoat 104 may be Nb₂O₅—ZrO₂.

According to embodiments of the present disclosure, overcoat 106 for SPGM catalyst system Type 1 100 may include aluminum oxide, doped aluminum oxide, zirconium oxide, doped zirconia, titanium oxide, tin oxide, silicon dioxide, zeolite, and mixtures thereof. According to the present disclosure, most suitable material for disclosed overcoat 106 may be alumina (Al₂O₃). Additionally, overcoat 106 for SPGM catalyst system Type 1 100 may include a PGM catalyst, such as Palladium (Pd), Platinum (Pt), Rhodium (Rh). According to the present disclosure, suitable PGM for disclosed overcoat 106 may be Pd.

FIG. 2 illustrates a PGM catalyst system configuration referred as PGM catalyst system Type 2 200, according to an embodiment.

As shown in FIG. 2, PGM catalyst system Type 2 200 may include at least a substrate 102, a washcoat 104, and an overcoat 106, where washcoat 104 may include doped ZrO2 and overcoat 106 may include carrier material oxides, such as alumina mixed with a PGM catalyst, such as Palladium (Pd).

In an embodiment, substrate 102 materials for PGM catalyst system Type 2 200 may include a refractive material, a ceramic material, a honeycomb structure, a metallic material, a ceramic foam, a metallic foam, a reticulated foam, or suitable combinations. According to the present disclosure, preferred substrate 102 materials may be ceramic material.

According to an embodiment, washcoat 104 for PGM catalyst system Type 2 200 may include support oxide such as zirconium oxide, doped zirconia. According to the present disclosure, suitable material for disclosed washcoat 104 may be Nb₂O₅—ZrO₂.

According to embodiments of the present disclosure, overcoat 106 for PGM catalyst system Type 2 200 may include aluminum oxide, doped aluminum oxide, zirconium oxide, doped zirconia, titanium oxide, tin oxide, silicon dioxide, zeolite, and mixtures thereof. According to the present disclosure, suitable material for disclosed overcoat 106 may be alumina (Al₂O₃). Additionally, overcoat 106 for PGM catalyst system Type 2 200 may include a PGM catalyst, such as Palladium (Pd).

According to embodiments of the present disclosure PGM catalyst system Type 2 200 has the same configuration as SPGM catalyst system Type 1 100 in which Cu—Mn spinel is removed from washcoat 104, in order to demonstrate the effect of addition of Cu—Mn spinel to PGM catalyst system Type 2 200.

Preparation of SPGM Catalyst System Type 1 (With Cu—Mn Spinel)

The preparation of washcoat 104 may begin by milling Nb₂O₅-Zr0₂support oxide to make aqueous slurry. The Nb₂O₅-Zr0₂support oxide may have Nb₂O₅loadings of about 15% to about 30% by weight, preferably about 25% and ZrO₂loadings of about 70% to about 85% by weight, preferably about 75%.

The Cu—Mn solution may be prepared by mixing for about 1 to 2 hours, an appropriate amount of Mn nitrate solution (Mn(NO₃)₂) and Cu nitrate solution (CuNO₃). Subsequently, Cu—Mn nitrate solution may be mixed with Nb₂O₅—ZrO₂support oxide slurry for about 2 to 4 hours, where Cu—Mn nitrate solution may be precipitated on Nb₂O₅—ZrO₂support oxide aqueous slurry. A suitable base solution may be added, such as to adjust the pH of the slurry to a suitable range. The precipitated Cu—Mn/Nb₂O₅—ZrO₂slurry may be aged for a period of time of about 12 to 24 hours under continued stirring at room temperature.

Subsequently, the precipitated slurry may be coated on substrate 102. The aqueous slurry of Cu—Mn/Nb₂O₅—ZrO₂may be deposited on the suitable ceramic substrate 102 to form washcoat 104, employing vacuum dosing and coating systems. In the present disclosure, a plurality of capacities of washcoat 104 loadings may be coated on the suitable ceramic substrate 102. The plurality of washcoat 104 loading may vary from about 60 g/L to about 200 g/L, in the present disclosure particularly about 120 g/L. Subsequently, after deposition on ceramic substrate 102 of the suitable loadings of Cu—Mn/Nb₂O₅—ZrO₂slurry, washcoat 104 may be dried overnight at about 120° C. and subsequently calcined at a suitable temperature within a range of about 550° C. to about 650° C., preferably at about 600° C. for about 5 hours. Treatment of washcoat 104 may be enabled employing suitable drying and heating processes. A commercially-available air knife drying systems may be employed for drying washcoat 104. Heat treatments (calcination) may be performed using commercially-available firing (furnace) systems.

Overcoat 106 may include a combination of Pd on alumina-based support. The preparation of overcoat 106 may begin by milling the alumina-based support oxide separately to make aqueous slurry. Subsequently, a solution of Pd nitrate may be mixed with the aqueous slurry of alumina with a loading within a range from about 0.5 g/ft³to about 10 g/ft³. Total loading of washcoat 104 material may be 120 g/L. After mixing of Pd and alumina slurry, Pd may be locked down with an appropriate amount of one or more base solutions, such as sodium hydroxide (NaOH) solution, sodium carbonate (Na₂CO₃) solution, ammonium hydroxide (NH₄OH) solution, tetraethyl ammonium hydroxide (TEAH) solution, among others. In the present embodiment, Pd may be locked down using a base solution of tetraethyl ammonium hydroxide (TEAH). Then, the resulting slurry may be aged from about 12 hours to about 24 hours for subsequent coating as overcoat 106 on washcoat 104, dried and fired at about 550° C. for about 4 hours.

Preparation of PGM Catalyst System Type 2 (Without Cu—Mn Spinel)

The preparation of washcoat 104 may begin by milling Nb₂O₅—ZrO₂support oxide to make aqueous slurry. The Nb₂O₅—ZrO₂support oxide may have Nb₂O₅loadings of about 15% to about 30% by weight, preferably about 25% and ZrO₂loadings of about 70% to about 85% by weight, preferably about 75%.

Subsequently, washcoat 104 slurry may be coated on substrate 102. The washcoat 104 slurry may be deposited on the suitable ceramic substrate 102 to form washcoat 104, employing vacuum dosing and coating systems. In the present disclosure, a plurality of capacities of washcoat 104 loadings may be coated on suitable ceramic substrate 102. The washcoat 104 loading may vary be of about 120 g/L. Washcoat 104 may be dried overnight at about 120° C. and subsequently calcined at a suitable temperature within a range of about 550° C. to about 650° C., preferably at about 550° C. for about 4 hours. Treatment of washcoat 104 may be enabled employing suitable drying and heating processes. A commercially-available air knife drying systems may be employed for drying washcoat 104. Heat treatments (calcination) may be performed using commercially-available firing (furnace) systems.

Overcoat 106 may include a combination of Pd on alumina-based support. The preparation of overcoat 106 may begin by milling the alumina-based support oxide separately to make aqueous slurry. Subsequently, a solution of Pd nitrate may be mixed with the aqueous slurry of alumina with a loading within a range from about 0.5 g/ft³to about 10 g/ft³. After mixing of Pd and alumina slurry, Pd may be locked down with an appropriate amount of one or more base solutions. In the present embodiment, Pd may be locked down using a base solution of tetraethyl ammonium hydroxide (TEAH). Then, the resulting slurry may be aged from about 12 hours to about 24 hours for subsequent coating as overcoat 106 on washcoat 104, dried and fired at about 550° C. for about 4 hours.

Catalytic performance, for SPGM Catalyst System Type 1 100 and PGM catalyst system Type 2 200 may be compared by preparing fresh and aged samples for each of the catalyst formulations and configurations in present disclosure to show the synergestic effect of adding Cu—Mn spinel to PGM catalyst materials which may be used in TWC applications.

In order to compare TWC performance of disclosed SPGM catalyst system Type 1 100 and PGM catalyst system Type 2 200, isothermal steady state sweep tests may be performed.

Additionally, in order to determine effect of Pd loadings on synergistic effect of Cu—Mn within SPGM Catalyst System Type 1 100, samples of SPGM Catalyst System Type 1 100 and PGM catalyst system Type 2 200 with different Pd loadings may be prepared, and isothermal steady state sweep tests may be performed.

Isothermal Steady State Sweep Test Procedure

The isothermal steady state sweep test may be carried out employing a flow reactor in which the inlet temperature may be increased to about 450° C., and testing a gas stream at 11-point R-values from about 2.0 (rich condition) to about 0.80 (lean condition) to measure the CO, NO, and HC conversions.

The space velocity (SV) in the flow reactor may be adjusted at about 40,000 h⁴. The gas feed employed for the test may be a standard TWC gas composition, with variable O₂concentration in order to adjust R-value from rich condition to lean condition during testing. The standard TWC gas composition may include about 8,000 ppm of CO, about 400 ppm of C₃H₆, about 100 ppm of C₃H₈, about 1,000 ppm of NO_R, about 2,000 ppm of H₂, 10% of CO₂, and 10% of H₂O. The quantity of O₂in the gas mix may be varied to adjust R-value which is representative of Air/Fuel (A/F) ratio.

EXAMPLES Example #1—Pd loading of 1 g/ft³

Example #1 catalyst system may be an SPGM Catalyst System Type 1 100, that includes an overcoat 106 with Pd loading of about 1 g/ft³.

Example #2—Pd loading of 1 g/ft³

Example #2 catalyst system may be a PGM catalyst system Type 2 200, that includes an overcoat 106 with Pd loading of about 1 g/ft³.

Example #3—Pd loading of 6 g/ft³

Example #3 catalyst system may be an SPGM Catalyst System Type 1 100, that includes an overcoat 106 with Pd loading of about 6 g/ft³.

Example #4—Pd loading of 6 g/ft³

Example #4 catalyst system may be a PGM catalyst system Type 2 200, that includes an overcoat 106 with Pd loading of about 6 g/ft³.

NOx conversion comparison of SPGM catalyst system Type 1 and PGM catalyst system Type 2

FIG. 3 depicts NOx conversion comparison 300 for fresh samples of SPGM catalyst system Type 1 100 including Example #1 catalyst system and Example #3 catalyst system; and PGM catalyst system Type 2 200, including Example #2 catalyst system and Example #4 catalyst system, under isothermal steady state sweep condition, at inlet temperature of about 450° C. and SV of about 40,000 h⁻¹, according to an embodiment.

As shown in FIG. 3A, NO conversion curve 302 (solid line) depicts performance of Example #1 catalyst system, and NO conversion curve 304 (dashed line) illustrates performance of Example #2 catalyst system; and in FIG. 3B NO conversion curve 306 (solid line) shows performance of Example #3 catalyst system, NO conversion curve 308 (dashed line) depicts performance of Example #4 catalyst system, all under isothermal steady state sweep condition.

As may be observed in NOx conversion comparison 300, disclosed SPGM catalyst, Example #1 catalyst system and Example #3 catalyst system, may perform better than disclosed PGM catalyst, Example #2 catalyst system and Example #4 catalyst system, because of their improved NO conversion under lean condition. For example, for very low loading of Pd, 1 g/ft̂3, as shown in FIG. 3A at lean condition, R-value of about 0.9, while SPGM catalyst, Example #1, shows NO conversion of about 96.15%, PGM catalyst, Example #2, shows NO conversion of about 12.7%. Furthermore, for low loading of Pd, 6 g/ft̂3, as shown in FIG. 3B at lean condition, R-value of about 0.9, while SPGM catalyst, Example #3, shows NO conversion of about 98.82%, PGM catalyst, Example #4, shows NO conversion of about 13.1%; moreover at R-value of about 0.8, while SPGM catalyst, Example #3, shows NO conversion of about 38.30%, PGM catalyst, Example #4, shows NO conversion of about 3.3%.

As may be observed in lean NOx conversion comparison 300 of fresh samples, there is an improved performance in NO conversion for disclosed SPGM catalysts, Example #1 catalyst system and Example #3 catalyst system, under lean condition (R-value<1.00) as compared to PGM catalysts, Example #2 catalyst system and Example #4 catalyst system. This improved performance of SPGM catalysts is the result of the synergistic effect between Pd, and the Cu—Mn spinel components in the respective compositions of both Example #1 catalyst system and Example #3 catalyst system, in which adding of Cu—Mn spinel components is responsible for the improved performance of NO conversion under lean condition compared with the level of NO conversion of Example #2 catalyst system and Example #4 catalyst system shown in NOx conversion comparison 300.

As may be observed in lean NOx conversion comparison 300, Example #3 catalyst system, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 6 g/ft³, exhibits higher catalytic activity than Example #1 catalyst system, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 1 g/ft3, showing that a higher Pd loading may result in an enhanced catalyst performance.

In addition, all fresh samples of SPGM catalyst system Type 1 100 and fresh samples of PGM catalyst system Type 2 200 present NO conversion of about 100% at R-value of about 1.00, which is the typical R-value for PGM catalysts.

FIG. 4 depicts NOx conversion comparison 400 for hydrothermally aged samples (at 900° C. during about 4 hours) of SPGM catalyst system Type 1 100 including Example #1 catalyst system and Example #3 catalyst system; and PGM catalyst system Type 2 200, including Example #2 catalyst system and Example #4 catalyst system, under isothermal steady state sweep condition, at inlet temperature of about 450° C. and SV of about 40,000 h⁻¹, according to an embodiment.

In FIG. 4A, NO conversion curve 402 (solid line) shows performance of Example #1 catalyst system, NO conversion curve 404 (dashed line) depicts performance of Example #2 catalyst system. In FIG. 4B NO conversion curve 406 (solid line) shows performance of Example #3 catalyst system, NO conversion curve 408 (dashed line) depicts performance of Example #4 catalyst system, all under isothermal steady state sweep condition.

As may be observed in NOx conversion comparison 400, SPGM catalyst, Example #1 catalyst system and Example #3 catalyst system , may perform better than PGM catalyst, Example #2 catalyst system and Example #4 catalyst system, because of their improved NO conversion under lean condition. For example, for very low loading of Pd, 1 g/ft̂3, as shown in FIG. 4A, at lean condition, R-value of about 0.9, SPGM catalyst, Example #1, shows NO conversion of about 80.4%, while PGM catalyst, Example #2, shows NO conversion of about 11%. Furthermore, for low loading of Pd, 6 g/ft̂3, as shown in FIG. 4B, at lean condition, R-value of about 0.9, SPGM catalyst, Example #3, shows NO conversion of about 97.8%, while PGM catalyst, Example #4, shows NO conversion of about 12.3%. As may be observed in NOx conversion comparison 400, SPGM catalysts, Example #3, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 6 g/ft³, exhibits higher catalytic activity than SPGM catalyst, Example #1, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 1 g/ft³, showing that a higher Pd loading may result in an enhanced catalyst performance.

As may be observed in lean NOx conversion comparison 400 of hydrothermally aged samples, there is an improved performance in NO conversion for disclosed SPGM catalysts, Example #1 catalyst system and Example #3 catalyst system, under lean condition (R-value<1.00) as compared to PGM catalysts, Example #2 catalyst system and Example #4 catalyst system. This improved performance of SPGM catalysts is the result of the synergistic effect between Pd, and the Cu—Mn spinel components in the respective compositions of both Example #1 catalyst system and Example #3 catalyst system, in which adding of Cu—Mn spinel components is responsible for the improved performance of NO conversion under lean condition compared with the level of NO conversion of Example #2 catalyst system and Example #4 catalyst system shown in NOx conversion comparison 400.

In addition, all samples of aged (at 900° C. during about 4 hours) SPGM catalyst system Type 1 100 and of aged (at 900° C. during about 4 hours) PGM catalyst system Type 2 200 present NO conversion of about 100% at R-value of about 1.00, which is the typical R-value for PGM catalysts, showing thermal stability of disclosed SPGM and PGM catalyst systems.

FIG. 5 depicts NOx conversion comparison 500 for fuel cut aged samples (aged at 800° C. during about 20 hours) of SPGM catalyst system Type 1 100 including Example #1 catalyst system and Example #3 catalyst system, and PGM catalyst system Type 2 200, including Example #2 catalyst system and Example #4 catalyst system, under isothermal steady state sweep condition, at inlet temperature of about 450° C. and SV of about 40,000 h⁻¹, according to an embodiment.

In FIG. 5A, NOx conversion comparison 500, NO conversion curve 502 (solid line) shows performance of Example #1 catalyst system, NO conversion curve 504 (dashed line) depicts performance of Example #2 catalyst system. In FIG. 5B, NO conversion curve 506 (solid line) shows performance of Example #3 catalyst system, NO conversion curve 508 (dashed line) depicts performance of Example #4 catalyst system, all under isothermal steady state sweep condition.

As may be observed in NOx conversion comparison 500, Example #1 catalyst system and Example #3 catalyst system may perform better than Example #2 catalyst system and Example #4 catalyst system because of their improved NO conversion. For example, for very low loading of Pd, 1 g/ft̂3, as shown in FIG. 5A, under rich condition, at R-value of about 1.3, while SPGM catalyst, Example 1 shows NO conversion of about 96.4%, PGM catalyst, Example #2, shows NO conversion of about 75%. Similarly, at more rich condition such as at R value of about 1.6, while SPGM catalyst, Example #1, shows NO conversion of about 98.6%, PGM catalyst, Example #2, shows NO conversion of about 24.9%. However, for loading of Pd of 6 gift³, as may be observed in FIG. 5B, a different behavior may observed. Improvement of NO conversion observed under lean condition, for example at R-value of about 0.9, while SPGM catalysts, Example #3, shows NO conversion of about 51.4%, PGM catalyst, Example #4, shows NO conversion of about 13.8%.

As may be observed in lean and rich NOx conversion comparison 500 of fuel cut aged samples, there is an improved performance in NO conversion for disclosed SPGM catalysts with very low Pd loading, Example #1 catalyst system, under rich condition as compared to PGM catalysts, Example #2. There is an improved performance in NO conversion for disclosed SPGM catalysts with higher Pd loading, Example #3 catalyst system, under lean condition (R-value<1.00) as compared to PGM catalysts, Example #4 catalyst system. This improved performance of SPGM catalysts is the result of the synergistic effect between Pd, and the Cu—Mn spinel components in the respective compositions of both Example #1 catalyst system and Example #3 catalyst system, in which adding of Cu—Mn spinel components is responsible for the improved performance of NO conversion under lean condition compared with the level of NO conversion of Example #2 catalyst system and Example #4 catalyst system shown in NOx conversion comparison 500.

CO Conversion Comparison of SPGM Catalyst System Type 1 and PGM Catalyst System Type 2

FIG. 6 depicts CO conversion comparison 600 for fresh and hydrothermally aged samples (at 900° C. during about 4 hours) of SPGM catalyst system Type 1 100 including Example # 1 catalyst system, and PGM catalyst system Type 2 200, including Example #2 catalyst system under isothermal steady state sweep condition, at inlet temperature of about 450° C. and SV of about 40,000 h⁻¹, according to an embodiment.

In FIG. 6A depicts CO conversion comparison 600 for fresh samples including CO conversion curve 602 (solid line) shows performance of Example #1 catalyst system, CO conversion curve 604 (dashed line) depicts performance of Example #2 catalyst system, and FIG. 6B depicts CO conversion comparison 600 for hydrothermally aged samples (at 900° C. during about 4 hours) including CO conversion curve 606 (solid line) shows performance of Example #1 catalyst system, CO conversion curve 608 (dashed line) depicts performance of Example #2 catalyst system, all under isothermal steady state sweep condition.

As may be observed in CO conversion comparison 600, under fresh and aged condition, SPGM catalyst, Example #1 catalyst system, may perform better than PGM catalyst, Example #2 catalyst system, because of their improved CO conversion under rich condition. For example, as shown in FIG. 6A for fresh samples, at fully rich condition, R-value of about 2.0, while SPGM catalyst, Example #1, shows CO conversion of about 80.2%, PGM catalyst, Example #2, shows CO conversion of about 60.8%. Furthermore for hydrothermal aged samples, as shown in FIG. 6B, at R-value of about 2.0, while SPGM catalyst, Example #1, shows CO conversion of about 84.1%, PGM catalyst, Example #2, shows CO conversion of about 41.6%. As may be observed in CO conversion comparison 600, for both fresh and aged samples, Example #1 catalyst system, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 1 g/ft³, exhibits higher catalytic activity than Example #2 catalyst system, that includes only an overcoat 106 with Pd loading of about 1 g/ft³.

As may be observed in CO conversion comparison 600, there is an improved performance in CO conversion for SPGM catalyst, Example #1, under both lean and rich condition as compared to PGM catalyst, Example #2, the improvement under rich condition is more significant. This improved performance is the result of the synergistic effect between the PGM components and the Cu—Mn spinel components in the respective compositions of Example #1 catalyst system, in which adding of Cu—Mn spinel components is responsible for the improved performance of CO conversion under rich condition compared with the level of CO conversion of Example #2 catalyst system shown in CO conversion comparison 600.

In addition, improvement of CO conversion for aged (at 900° C. during about 4 hours) SPGM catalyst system Type 1 100, Example #1, compared to PGM catalysts system Type 2 200, Example#2, depicts the thermal stability of disclosed SPGM catalyst.

FIG. 7 depicts CO conversion comparison 700 in CO conversion for fuel cut aged samples (at 800° C. during about 20 hours) of SPGM catalyst system Type 1 100 including Example # 1 catalyst system and Example #3 catalyst system, and PGM catalyst system Type 2 200, including Example #2 catalyst system and Example #4 catalyst system, under isothermal steady state sweep condition, at inlet temperature of about 450° C. and SV of about 40,000 h⁻¹, according to an embodiment.

In FIG. 7A, CO conversion curve 702 (solid line) shows performance of Example #1 catalyst system, CO conversion curve 704 (dashed line) depicts performance of Example #2 catalyst system, and in FIG. 7B, CO conversion curve 706 (solid line) shows performance of Example #3 catalyst system, CO conversion curve 708 (dashed line) depicts performance of Example #4 catalyst system, all under isothermal steady state sweep condition.

As may be observed in CO conversion comparison 700, SPGM catalyst, Example #1 catalyst system and Example #3 catalyst system may perform better than PGM catalyst, Example #2 catalyst system and Example #4 catalyst system, because of their improved CO conversion under rich condition. For example, for very low loading of Pd, 1 g/ft̂3, as shown in FIG. 7A, at rich condition, R-value of about 1.5, while SPGM catalyst, Example #1, shows CO conversion of about 87.9%, PGM catalyst, Example #2, shows CO conversion of about 40.2%. Similarly, at R-value of about 2.0, while SPGM catalyst shows CO conversion of about 81%, PGM catalyst shows CO conversion of about 15.9%. Furthermore, for low loading of Pd, 6 gift̂3, as shown in FIG. 7B, at rich condition, R-value of about 1.5, while SPGM catalyst system shows CO conversion of about 91.6%, PGM catalyst shows CO conversion of about 56.2%. Similarly, at R-value of about 2.0, while SPGM catalyst system shows CO conversion of about 88.9%, PGM catalyst shows CO conversion of about 28.2%. As may be observed in CO conversion comparison 700, Example #3 catalyst system, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 6 g/ft³, exhibits higher catalytic activity than Example #1 catalyst system, that includes Cu—Mn spinel and an overcoat 106 with Pd loading of about 1 g/ft³, showing that a higher Pd loading may result in an enhanced catalyst performance.

As may be observed in CO conversion comparison 700, there is an improved performance in CO conversion for SPGM catalyst, Example #1 and Example #3, under both lean and rich condition of stoichiometric as compared to PGM catalyst, Example #2 and Example #4. This improved performance which is more significant under rich condition is the result of the synergistic effect between the Pd components and the Cu—Mn spinel components in the respective compositions of both Example #1 catalyst system and Example #3 catalyst system, in which adding of Cu—Mn spinel components is responsible for the improved performance of CO conversion under rich condition compared with the level of CO conversion of Example #2 catalyst system and Example #4 catalyst system shown in CO conversion comparison 700.

As may be observed in performance comparison between SPGM catalyst system Type 1 100 and PGM catalyst system Type 2 200, there is a significant improved performance in NO conversion under lean conditions for disclosed SPGM catalyst system Type 1 100. This improved performance is the result of the synergistic effect between the PGM component (palladium) and the ZPGM components (Cu—Mn stoichiometric spinel) in the respective compositions of disclosed SPGM catalyst system Type 1 100, in which adding of ZPGM components is responsible for the improved performance of NO conversion when compared with the level of NO conversion of the PGM catalyst shown in PGM NO conversion curve 402. Therefore, SPGM catalyst system Type 1 100 exhibits a higher level NO conversion than PGM catalyst system Type 2 200. Since high performance under lean operating conditions allows less fuel consumption, then vehicles may employ disclosed SPGM catalyst system Type 1 100 to achieve better fuel economy.

Furthermore, synergistic effect of Cu—Mn on Pd results is improvement of CO conversion under both lean and rich conditions. The improvement is more significant under rich condition. Moreover, isothermal steady state tests results showed that higher Pd loading may also contribute to an enhanced catalytic activity. In addition, the significant improvement of NO and CO conversion under lean-rich condition of disclosed SPGM catalyst after hydrothermal and fuel cut aging shows thermal stability of disclosed SPGM catalyst systems, in which synergistic effect of Cu—Mn is responsible for such stability.

While various aspects and embodiments have been disclosed, other aspects and embodiments may be contemplated. The various aspects and embodiments disclosed here are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

1. A synergized platinum group metal (SPGM) catalyst system which exhibits high catalytic activity under both lean condition and rich condition, comprising:

at least one substrate;

at least one washcoat comprising at least one oxygen storage material further comprising Cu—Mn spinel having a niobium-zirconia support oxide; and

at least one overcoat comprising at least one palladium group metal catalyst and Al2O3;

wherein the at least one palladium group metal catalyst has a concentration of about 6 g/ft3 to about 1 g/ft3; and

wherein NOx conversion is higher as compared to a palladium group metal catalyst having substantially no Cu—Mn spinel.

2. The catalyst system of claim 1, wherein the Cu—Mn spinel comprises CuMn2O4.

3. The catalyst system of claim 1, wherein the Cu—Mn spinel is stoichiometric.

4. The catalyst system of claim 1, wherein the niobium-zirconia support oxide comprises Nb2O5—ZrO2,

5. The catalyst system of claim 1, further comprising at least one impregnation layer.

6. The catalyst system of claim 1, wherein the at least one substrate comprises a ceramic.

7. The catalyst system of claim 1, wherein the conversion of NOx is substantially complete under lean exhaust conditions.

8. The catalyst system of claim 1, wherein the conversion of CO is substantially complete under lean exhaust conditions.

9. The catalyst system of claim 1, wherein the conversion of NOx is near 95% under lean exhaust conditions.

10. The catalyst system of claim 1, wherein the NOx R-value is about 0.950.

11. The catalyst system of claim 1, wherein the NOx R-value is about 1.0

12. The catalyst system of claim 1, wherein the niobium-zirconia support oxide comprises about 15% to about 30% by weight Nb2O5.

13. The catalyst system of claim 1, wherein the niobium-zirconia support oxide comprises about 25% by weight Nb2O5.

14. The catalyst system of claim 1, wherein the niobium-zirconia support oxide comprises about 70% to about 85% ZrO2,

15. The catalyst system of claim 1, wherein the niobium-zirconia support oxide comprises about 75% ZrO2.