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This paper, written in collaboration with Ford, evaluates the effectiveness of higher cell density combined with higher porosity, lower thermal mass substrates for emission control capability on a customized, RDE (Real Driving Emissions)-type of test cycle run on a chassis dynamometer using a gasoline passenger car fitted with a three-way catalyst (TWC) system. Cold-start emissions contribute most of the emissions control challenge, especially in the case of a very rigorous cold-start. The majority of tailpipe emissions occur during the first 30 seconds of the drive cycle. For the early engine startup phase, higher porosity substrates are developed as one part of the solution. In addition, further emission improvement is expected by increasing the specific surface area (GSA) of the substrate. This test was designed specifically to stress the cold start performance of the catalyst by using a short, 5 second idle time preceding an aggressive, high exhaust mass flowrate drive cycle.

Gasoline particulate filters (GPF) with high filtration efficiency (>80%) at zero mileage are in growing demand to meet increasingly tight vehicle emission standards for particulate matter being implemented in US, EU, China and elsewhere. Current efforts to achieve high filter performance mainly focus on fine-tuning the filter structure, such as the pore size distribution and porosity of the bare substrate, or the washcoat loading and location of catalyzed substrates. However, high filtration efficiency may have a cost in high backpressure that negatively affects engine power. On the other hand, it has been recognized in a few reports that very low amounts of ash deposits (from non-combustible residue in the exhaust) can significantly increase filtration efficiency with only a mild backpressure increase.

The need for gasoline particulate filter (GPF) technology is expected to grow with increasingly tight particle emissions standards being implemented in US, EU, China and elsewhere. Derived from the successful experience with diesel particulate filters (DPF), GPFs adopted the characteristic alternately plugged honeycomb structure that provides a large area of porous cordierite wall for filtering particles with minimal additional backpressure. However, unlike DPFs, continuous soot regeneration in GPFs makes it difficult to grow and sustain the soot cake on the filter wall that gives DPFs their high filtration efficiency. Therefore, filtration performance of low mileage GPFs relies heavily on the porous structure of filter media, which depends on both the substrate and the applied washcoat. In this work, a blank, two fresh washcoated filters and two washcoated filters with 3000 km mileage accumulation were characterized to compare their filtration performance.

It is anticipated that future gasoline engines will have improved mechanical efficiency and consequently lower exhaust temperatures at low load conditions, although the exhaust temperatures at high load conditions are expected to remain the same or even increase due to the increasing use of downsized turbocharged engines. In 2014, a collaborative project was initiated at Ford Motor Company, Oak Ridge National Lab, and the University of Michigan to develop three-way catalysts with improved performance at low temperatures while maintaining the durability of current TWCs. This project is funded by the U.S. Department of Energy and is intended to show progress toward the USDRIVE target of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150 °C after high mileage aging. The testing protocols specified by the USDRIVE ACEC team for stoichiometric S-GDI engines were utilized during the evaluation of experimental catalysts at all three facilities.

To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.

With an emerging need for gasoline particulate filters (GPFs) to lower particle emissions from gasoline direct injection (GDI) engines, studies are being conducted to optimize GPF designs in order to balance filtration efficiency, backpressure penalty, filter size, cost and other factors. Metal fiber filters could offer additional designs to the GPF portfolio, which is currently dominated by ceramic wall-flow filters. However, knowledge on their performance as GPFs is still limited. In this study, modeling on backpressure and filtration efficiency of fibrous media was carried out to determine the basic design criteria (filtration area, filter thickness and size) for different target efficiencies and backpressures at given gas flow conditions. Filter media with different fiber sizes (8 - 17 μm) and porosities (80% - 95%) were evaluated using modeling to determine the influence of fiber size and porosity.

Model low temperature NOx adsorbers (LTNA) consisting of Pd on a ceria/zirconia washcoat on monoliths were evaluated for low temperature NOx storage under lean conditions to assess their potential for adsorbing the cold-start NOx emissions on a diesel engine during the period before the urea/SCR system becomes operational. A reactor-based transient test was performed with and without C2H4, CO/H2, and H2O to assess the effects of these species on the NOx storage performance. In the absence of C2H4 or CO/H2, H2O severely suppressed the NOx storage of these model LTNAs at temperatures below 100°C, presumably by blocking the storage sites. When C2H4 was included in the feedgas, H2O still suppressed the NOx storage below 100°C. However, the C2H4 significantly increased the NOx storage efficiency above 100°C, attributable to the formation of alkyl nitrites or alkyl nitrates on the catalyst.

In anticipation that future gasoline engines will have improved fuel efficiency and therefore lower exhaust temperatures during low load operation, a project was initiated in 2014 to develop three-way catalysts (TWC) with improved activity at lower temperatures while maintaining the durability of current TWCs. This project is a collaboration between Ford Motor Company, Oak Ridge National Laboratory, and the University of Michigan and is funded by the U.S. Department of Energy. The ultimate goal is to show progress towards the USDRIVE goal of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150°C after high mileage aging. A reactor was set up at Ford to follow the catalyst testing protocols established by the USDRIVE ACEC tech team for evaluating catalysts for stoichiometric gasoline direct-injection (S-GDI) engines; this protocol specifies a stoichiometric blend of CO/H2, NO, C3H6, C2H4, C3H8, O2, H2O, and CO2 for the evaluations.

The purpose of this work was to examine gasoline particle filters (GPFs) at high mileages. Soot levels for gasoline direct injection (GDI) engines are much lower than diesel engines; however, noncombustible material (ash) can cause increased backpressure, reduced power, and lower fuel economy. In this study, a post mortem was completed of two GPFs, one at 130,000 mi and the other at 150,000 mi, from two production 3.5L turbocharged GDI vehicles. The GPFs were ceramic wall-flow filters containing three-way catalytic washcoat and located downstream of conventional three-way catalysts. The oil consumption was measured to be approaching 23,000 mpqt for one vehicle and 30,000 mpqt for the other. The ash contained Ca, P, Zn, S, Fe, and catalytic washcoat. Approximately 50 wt% of the collected ash was non-lubricant derived. The filter capture efficiency of lubricant-derived ash was about 50% and the non-lubricant metal (mostly Fe) deposition rate was 0.9 to 1.2 g per 10,000 mi.

The increasing use of gasoline direct injection (GDI) engines coupled with the implementation of new particulate matter (PM) and particle number (PN) emissions regulations requires new emissions control strategies. Gasoline particulate filters (GPFs) present one approach to reduce particle emissions. Although primarily composed of combustible material which may be removed through oxidation, particle also contains incombustible components or ash. Over the service life of the filter the accumulation of ash causes an increase in exhaust backpressure, and limits the useful life of the GPF. This study utilized an accelerated aging system to generate elevated ash levels by injecting lubricant oil with the gasoline fuel into a burner system. GPFs were aged to a series of levels representing filter life up to 150,000 miles (240,000 km). The impact of ash on the filter pressure drop and on its sensitivity to soot accumulation was investigated at specific ash levels.

Lean NOx Traps (LNTs) are one type of lean NOx reduction technology typically used in smaller diesel passenger cars where urea-based Selective Catalytic Reduction (SCR) systems may be difficult to package . However, the performance of lean NOx traps (LNT) at temperatures above 400 C needs to be improved. The use of Rapidly Pulsed Reductants (RPR) is a process in which hydrocarbons are injected in rapid pulses ahead of a LNT in order to expand its operating window to higher temperatures and space velocities. This approach has also been called Di-Air (diesel NOx aftertreatment by adsorbed intermediate reductants) by Toyota. There is a vast parameter space which could be explored to maximize RPR performance and reduce the fuel penalty associated with injecting hydrocarbons. In this study, the mixing uniformity of the injected pulses, the type of reductant, and the concentration of pulsed reductant in the main flow were investigated.

U.S. federal vehicle emission standards effective in 2007 require tight control of NOx and hydrocarbon emissions. For light-duty vehicles, the current standard of Tier 2 Bin 5 is about 0.07 g/mi NOx and 0.09 g/mi NMOG (non-methane organic gases) at 120,000 mi. However, the proposed future standard is 0.03 g/mi for NMOG + NOx (~SULEV30) at 150,000 mi. There is a significant improvement needed in catalyst system efficiencies for diesel vehicles to achieve the future standard, mainly during cold start. In this study, a less than 6000 lbs diesel truck equipped with an advanced urea Selective Catalytic Reduction (SCR) system was used to pursue lower tailpipe emissions with an emphasis on vehicle calibration and catalyst package. The calibration was tuned by optimizing exhaust gas recirculation (EGR) fuel injection and cold start strategy to generate desirable engine-out emissions balanced with reasonable temperatures.

An advanced diesel aftertreatment system utilizing Selective Catalytic Reduction (SCR) with urea for lean nitrogen oxides (NOx) control was tested on a 2.7L V6 Land Rover vehicle to demonstrate the capability of achieving Tier 2 Bin 5 and lower emission standards for light-duty trucks. SCR washcoat was applied to a diesel particulate filter (DPF) to perform NOx and particulate reduction simultaneously. Advanced SCR systems employed both traditional SCR catalysts and SCR-coated filters (SCRF) to improve the NOx reduction efficiency. The engine-out NOx level was adjusted by modifying the EGR (Exhaust Gas Recirculation) calibration. Cold start NOx performance was improved by SCR warm-up strategy and urea over injection. This study showed the advanced SCR system could tolerate higher NH₃ storage in the SCR catalyst, resulting in overall higher NOx conversion on the FTP-75 test cycle.

A 2005 prototype diesel aftertreatment system consisting of diesel oxidation catalysts (DOC), Cu/zeolite Selective Catalytic Reduction (SCR) catalyst, and Catalyzed Diesel Particulate Filter (CDPF) was aged to an equivalent of 120k mi on an engine dynamometer using an aging cycle that incorporated both city and highway driving modes. The program demonstrated durable reduction in particulate matter (PM) and nitrogen oxides (NOx) emissions to federal Tier 2 levels on a 6000 lbs light-duty truck application. Very low sulfur diesel fuel (∼15 ppm) enabled lower PM emissions, reduced the fuel penalty associated with the emission control system, and improved long-term system durability. A total of 643 filter regenerations occurred during the aging that raised the entire catalyst system to high temperatures on a regular basis. After testing the aged system on a 6000 lbs light-duty diesel truck, a post mortem analysis was completed on core samples taken from the DOC, SCR catalyst, and filter.

Selective Catalytic Reduction (SCR) catalysts have been designed to reduce NOx with the assistance of an ammonia-based reductant. Diesel Particulate Filters (DPF) have been designed to trap and eventually oxidize particulate matter (PM). Combining the SCR function within the wall of a high porosity particulate filter substrate has the potential to reduce the overall complexity of the aftertreatment system while maintaining the required NOx and PM performance. The concept, termed Selective Catalytic Reduction Filter (SCRF) was studied using a synthetic gas bench to determine the NOx conversion robustness from soot, coke, and hydrocarbon deposition. Soot deposition, coke derived from propylene exposure, and coke derived from diesel fuel exposure negatively affected the NOx conversion. The type of soot and/or coke responsible for the inhibited NOx conversion did not contribute to the SCRF backpressure.

High gas prices combined with demand for improved fuel economy have prompted increased interest in diesel engine applications for both light-duty and heavy-duty vehicles. The development of aftertreatment systems for these vehicles requires significant investments of capital and time. A reliable and robust qualification testing procedure will allow for more rapid development with lower associated costs. Qualification testing for DPFs has its basis in methods similar to DOCs but also incorporates a PM loading method and regeneration testing of loaded samples. This paper examines the effects of accelerated loading using a PM generator and compares PM generator loaded DPFs to engine dynamometer loaded samples. DPFs were evaluated based on pressure drop and regeneration performance for samples loaded slowly and for samples loaded under accelerated conditions. A regeneration reactor was designed and built to help evaluate the DPFs loaded using the PM generator and an engine dynamometer.

Urea selective catalytic reduction (SCR) catalysts have the capability to deliver the high NOx conversion efficiencies required for future emission standards. However, the potential for the occasional over-temperature can lead to the irreversible deactivation of the SCR catalyst. On-board diagnostics (OBD) compliance requires monitoring of the SCR function to make sure it is operating properly. Initially, SCR catalyst performance metrics such as NOx conversion, NH3 oxidation, NH3 storage capacity, and BET surface area are within normal limits. However, these features degrade with high temperature aging. In this work, a laboratory flow reactor was utilized to determine the impact on these performance metrics as a function of aging condition. Upon the completion of a full time-at-temperature durability study, four performance criteria were established to help determine a likely SCR failure.

For diesel applications, cold start accounts for a large amount of the total NOx emissions during a typical Federal Test Procedure (FTP) for light-duty vehicles and is a key focus for reducing NOx emissions. A common form of diesel NOx aftertreatment is selective catalytic reduction (SCR) technology. For cold start NOx improvement, the SCR catalyst would be best located as the first catalyst in the aftertreatment system; however, engine-out hydrocarbons and no diesel oxidation catalyst (DOC) upstream to generate an exotherm for desulfation can result in degraded SCR catalyst performance. Recent advances in vanadia-based SCR (V-SCR) catalyst technology have shown better low temperature NOx performance and improved thermal durability. Three V-SCR technologies were tested for their thermal durability and low-temperature NOx performance, and after 600°C aging, one technology showed low-temperature performance on par with state-of-the-art copper-zeolite SCR (Cu-SCR) technology.

Selective catalytic reduction (SCR) is expected to be used extensively in the U.S. for diesel vehicle NOx control. Much progress has been made on improving performance and reducing complexity of SCR systems for vehicles in the past several years. SCR system complexity can be reduced further by implementation of SCR-coated diesel particulate filters (SCRFs). In this system, a high porosity (> 50%) filter substrate is coated with an SCR formulation, ideally in the pores of the filter walls, so that the DPF and SCR functions can be combined into a single catalyst. Two state-of-the-art Cu/zeolite SCR formulations and three types of high porosity filter substrates were included in this study. Laboratory and engine-dynamometer tests were performed to measure NOx conversion under a variety of conditions to assess the impact of ammonia oxidation, inlet NO2/NOx ratio, ammonia/NOx ratio, oxygen level, space velocity, soot loading, and ammonia loading level.

Copper/zeolite catalysts are the leading urea SCR catalysts for NOx emission treatment in diesel applications. Sulfur poisoning directly impacts the overall SCR performance and is still a durability issue for Cu/zeolite SCR catalysts. Most studies on sulfur poisoning of Cu/zeolite SCR catalysts have been based on SO2 as the poisoning agent. It is important to investigate the relative poisoning effects of SO3, especially for systems with DOCs in front of Cu/zeolite SCR catalysts. It was observed that SCR activity was significantly reduced for samples poisoned by SO3 vs. those poisoned by SO2. The sulfur was released mainly as SO2 for both samples poisoned by SO2 and SO3. The temperatures and the magnitudes of released SO2 peaks however, were very different between the samples poisoned by SO2 vs. SO3. The results indicate that sulfur poisoning by SO2 and SO3 are not equivalent, with different poisoning mechanisms and impacts.