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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.

It is likely that use of urea-based selective catalytic reduction (SCR) will be needed to meet U.S. Tier 2 diesel emission standards for oxides of nitrogen (NOx). The ideal ratio of ammonia (NH3) molecules to NOx molecules (known as alpha) is 1:1 based on urea consumption and having NH3 available for reaction of all of the exhaust NOx. However, SCR efficiency can be less than 100% at low temperatures in general, and at higher temperatures with high exhaust SCR catalyst space velocities. At the low temperatures where NOx conversion efficiency is low, it may be advantageous to reduce the alpha ratio to values less than one (less NH3 than is needed to convert 100% of the NOx emissions) to avoid NH3 slip. At higher space velocities and high temperatures, the NOx conversion efficiency may be higher with alpha ratios greater than 1. There is however concern that the additional NH3 will be slipped under these conditions.

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.

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.

Selective Catalytic Reduction of NOx is a promising technology to enable diesel engines to meet certification under Tier 2 Bin 5 emissions requirements. SCR catalysts for vehicle use are typically zeolitic materials known to store both hydrocarbons and ammonia. Ammonia storage on the zeolite has a beneficial effect on NOx conversion; hydrocarbons however, compete with ammonia for storage sites and may also block access to the interior of the zeolites where the bulk of the catalytic processes take place. This paper presents the results of laboratory studies utilizing surrogate hydrocarbon species to simulate engine-out exhaust over catalysts formulated to operate in both low (≈175-500°C) and high temperature (≈250-600°C) regimes. The effects of hydrocarbon exposure of these individual species on the SCR reaction are examined and observations are made as to necessary conditions for the recovery of SCR activity.

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.

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.

Selective catalytic reduction (SCR) is a promising technology for diesel aftertreatment to meet NOx emissions targets in several countries. In established markets such as the US and Europe, zeolite SCR systems are expected to be used due to their ability to survive the exhaust gas temperatures seen in an active diesel particulate filter regeneration. In emerging markets where the fuel sulfur level may be as high as 2000 parts per million, zeolite SCR catalysts may have durability issues. In these markets, low sulfur fuel is needed overall to meet emissions standards and to avoid high sulfate emissions, but the aftertreatment system must be durable to high sulfur levels because there is a risk of exposure to high sulfur fuel. Also, emissions standards may be met without a DPF in some applications, so that the exhaust system would not see temperatures of 600°C or higher.

The 2007 emission standards for both light-duty and heavy-duty diesel vehicles remain a challenge. A level of about 90% NOx conversion is required to meet the standards. Technologies that have the most potential to achieve very high NOx conversion at low temperatures of diesel exhaust are lean NOx traps (LNTs) and Selective Catalytic Reduction (SCR) of NOx using aqueous urea, typically known as Urea SCR. The LNT has the advantage of requiring no new infrastructure, and does not pose any new customer compliance issues. However, Urea SCR has high and durable NOx conversion in a wider temperature window, a lower equivalent fuel penalty, and lower system cost. On a technical basis, Urea SCR has the best chance of meeting the 2007 NOx targets. This paper reviews the results of some demonstration programs for both light-and heavy-duty applications.

Base metal/zeolite catalysts, particularly containing copper and iron, are among the leading candidates for treatment of NOx emissions for diesel applications. Even with the use of ultra low sulfur fuel, sulfur poisoning is still a durability issue for base metal/zeolite SCR catalysts. In this study, the impact of sulfur poisoning on SCR activity and the stored sulfur removal effectiveness were investigated on several Cu and Fe/zeolite SCR catalysts after different thermal aging. The impact of sulfur was more significant on the Cu than on Fe/zeolite SCR catalysts for the NOx activity. It was found that the sensitivity of thermal aging status to the sulfur poisoning impact was different. The impact of sulfur on NOx activity changed with thermal aging on some catalysts, while it remained relatively the same for other catalysts. The most thermally durable SCR catalyst was not necessarily the most durable to sulfur poisoning.

The accumulation of soot and lubrication-derived ash particles in a diesel particulate filter (DPF) increases exhaust flow restriction and negatively impacts engine efficiency. Previous studies have described the macroscopic phenomenon and general effects of soot and ash accumulation on filter pressure drop. In order to enhance the fundamental understanding, this study utilized a novel apparatus that of a dual beam scanning electron microscope (SEM) and focused ion beam (FIB), to investigate microscopic details of soot and ash accumulation in the DPF. Specifically, FIB provides a minimally invasive technique to analyze the interactions between the soot, ash, catalyst/washcoat, and DPF substrate with a high degree of measurement resolution. The FIB utilizes a gallium liquid metal ion source which produces Ga+ ions of sufficient momentum to directionally mill away material from the soot, ash, and substrate layers on a nm-μm scale.

Current CJ-4 lubricant specifications place chemical limits on diesel engine oil formulations to minimize the accumulation of lubricant-derived ash in diesel particulate filters (DPF). While lubricant additive chemistry plays a strong role in determining the amount and type of ash accumulated in the DPF, a number of additional factors play important roles as well. Relative to soot particles, whose residence time in the DPF is short-lived, ash particles remain in the filter for a significant fraction of the filter's useful life. While it is well-known that the properties (packing density, porosity, permeability) of soot deposits are primarily controlled by the local exhaust conditions at the time of particle deposition in the DPF, the cumulative operating history of the filter plays a much stronger role in controlling the properties and distribution of the accumulated ash.

Radio frequency (RF)-based sensors provide a direct measure of the particulate filter loading state. In contrast to particulate matter (PM) sensors, which monitor the concentration of PM in the exhaust gas stream for on-board diagnostics purposes, RF sensors have historically been applied to monitor and control the particulate filter regeneration process. This work developed an RF-based particulate filter control system utilizing both conventional and fast response RF sensors, and evaluated the feasibility of applying fast-response RF sensors to provide a real-time measurement of engine-out PM emissions. Testing with a light-duty diesel engine equipped with fast response RF sensors investigated the potential to utilize the particulate filter itself as an engine-out soot sensor.

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.

Diesel Particulate Filters (DPF) are a key component in many on- and off-road aftertreatment systems to meet increasingly stringent particle emissions limits. Efficient thermal management and regeneration control is critical for reliable and cost-effective operation of the combined engine and aftertreatment system. Conventional DPF control systems predominantly rely on a combination of filter pressure drop measurements and predictive models to indirectly estimate the soot loading state of the filter. Over time, the build-up of incombustible ash, primarily derived from metal-containing lubricant additives, accumulates in the filter to levels far exceeding the DPF's soot storage limit. The combined effects of soot and ash build-up dynamically impact the filter's pressure drop response, service life, and fuel consumption, and must be accurately accounted for in order to optimize engine and aftertreatment system performance.

Efficient aftertreatment management requires accurate sensing of both particulate filter soot and ash levels for optimized feedback control. Currently a combination of pressure drop measurements and predictive models are used to indirectly estimate the loading state of the filter. Accurate determination of filter soot loading levels is challenging under certain operating conditions, particularly following partial regeneration events and at low flow rate (idle) conditions. This work applied radio frequency (RF)-based sensors to provide a direct measure of the particulate filter soot levels in situ. Direct measurements of the filter loading state enable advanced feedback controls to optimize the combined engine and aftertreatment system for improved DPF management. This study instrumented several cordierite and aluminum titanate diesel particulate filters with RF sensors. The systems were tested on a range of light- and heavy-duty applications, which included on- and off-road engines.

Diesel vehicles have significant advantages over their gasoline counterparts including a more efficient engine, higher fuel economy, and lower emissions of HC, CO, and CO2. However, NOx control is more difficult on a diesel because of the high O2 concentration in the exhaust, making conventional three-way catalysts ineffective. Two current available technologies for continuous NOx reduction onboard diesel vehicles are Selective Catalytic Reduction (SCR) using aqueous urea and lean NOx trap (LNT) catalysts. This paper discusses an application with SCR. SCR with ammonia has been used for many years at stationary sources. Aqueous urea is a convenient way to deliver ammonia onboard a vehicle and high NOx efficiencies have been shown in past work by Ford and others using urea. Tailpipe NOx emissions from a modified European production level 1.8L diesel Ford Focus TDCi were reduced to the range of ULEVII levels (0.05 g/mi NOx) with a green catalyst system.

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.

Accurate knowledge of diesel particulate filter (DPF) particulate matter (PM) loading is critical for robust and efficient operation of the combined engine-exhaust aftertreatment system. Furthermore, upcoming on-board diagnostics regulations require on-board technologies to evaluate the status of the DPF. This work describes the application of radio frequency (RF) - based sensing techniques to accurately measure DPF particulate matter levels. A 1.9L GM turbo diesel engine and a DPF with an RF-sensor were studied. Direct comparisons between the RF measurement and conventional pressure-based methods were made. Further analysis of the particulate matter loading rates was obtained with a mass-based total PM emission measurement instrument (TEOM) and DPF gravimetric measurements.

Diesel exhaust systems equipped with selective catalytic reduction (SCR) catalysts based on urea were subjected to an aging process where the exhaust gas temperature was below 300°C. Solid deposits related to urea injection were found on the wall of the exhaust pipe down stream of the urea injector and on a urea mixer in front of the SCR catalyst. In laboratory tests, an aqueous solution of urea (1.5wt%) was dripped onto an SCR catalyst core in a simulated lean gas mixture at a rate corresponding to a 1:1 NH3-to-NOx ratio (NOx = 350ppm) and a space velocity (SV) of 15,000 h-1 at various temperatures. At 300°C and below, urea-related deposits appeared on the SCR catalyst surface and totally plugged the SCR catalyst monolith within 250 hours. When the aging temperature was 350°C or above, no deposits were observed on the SCR catalyst core.