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A laboratory study was performed to assess the effects of sulfur poisoning and desulfation temperature on the NO conversion of a LNT+(Cu/SCR) in-situ system. Four LNT+(Cu/SCR) systems were aged for 4.5 hours without sulfur at 600, 700, 750, and 800°C using A/F ratio modulations to represent 23K miles of desulfations at different temperatures. NO conversion tests were performed on the LNT alone and on the LNT+SCR system using a 60 s lean/5 s rich cycle. The catalysts were then sulfur-poisoned at 400°C and desulfated four times and re-evaluated on the 60/5 tests. This test sequence was repeated 3 more times to represent 100K miles of desulfations. After simulating 23K miles of desulfations, the Cu-based SCR catalysts improved the NO conversion of the LNT at low temperatures (e.g., 300°C), although the benefit decreased as the desulfation temperature increased from 600°C to 800°C.

New European emissions legislation (Euro5) specifies a limit for Particle Number (PN) emissions and therefore drives measurement of PN during vehicle development and homologation. Concurrently, the use of biofuel is increasing in the marketplace, and Euro5 specifies that reference fuel must contain a bio-derived portion. Work was carried out to test the effect of fuels containing different levels of Fatty Acid Methyl Ester (FAME) on particle number, size, mass and composition. Measurements were conducted with a Cambustion Differential Mobility Spectrometer (DMS) to time-resolve sub-micron particles (5-1000nm), and a Horiba Solid Particle Counting System (SPCS) providing PN data from a Euro5-compliant measurement system. To ensure the findings are relevant to the modern automotive business, testing was carried out on a Euro4 compliant passenger car fitted with a high-pressure common-rail diesel engine and using standard homologation procedures.

Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.

This study extends research previously reported from our laboratory [SAE 2009-01-0285] on diesel NOx control utilizing a new generation of Lean NOx Trap (LNT) plus in-situ Selective Catalytic Reduction (SCR) catalyst systems. Key findings from this work include 1) evidence for a “non-ammonia” reduction pathway over the SCR catalyst (in addition to the conventional ammonia pathway), 2) high NOx conversions utilizing LNT formulations with substantially lower platinum group metal (PGM) loadings than utilized in earlier systems, 3) ability of the downstream SCR catalyst to maintain high overall system NOx efficiency with aged LNTs, and 4) effectiveness of both Cu- and Fe-zeolite SCR formulations to enhance overall system NOx efficiency. FTP NOx conversion efficiencies in excess of 95% were obtained on two light-duty vehicle platforms with lab-aged catalyst systems, thus showing potential of the LNT+SCR approach for achieving the lowest U.S. emissions standards

Modern diesel engines employ a multitude of strategies for oxides of nitrogen (NOx) emission abatement, with exhaust gas recirculation (EGR) being one of the most effective technique. The need for a precise control on the intake charge dilution (as a result of EGR) is paramount since small fluctuations in the intake charge dilution at high EGR rates may cause larger than acceptable spikes in NOx/soot emissions or deterioration in the combustion efficiency, especially at low to mid-engine loads. The control problem becomes more pronounced during transient engine operation; currently the trend is to momentarily close the EGR valve during tip-in or tip-out events. Therefore, there is a need to understand the transient EGR behaviour and its impact on the intake charge development especially under unstable combustion regimes such as low temperature combustion.

Aftertreatment system design involves multiple tradeoffs between engine performance, fuel economy, regulatory emission levels, packaging, and cost. Selection of the best design solution (or “architecture”) is often based on an assumption that inherent catalyst activity is unaffected by location within the system. However, this study acknowledges that catalyst activity can be significantly impacted by location in the system as a result of varying thermal exposure, and this in turn can impact the selection of an optimum system architecture. Vehicle experiments with catalysts aged over a range of mild to moderate to severe thermal conditions that accurately reflect select locations on a vehicle were conducted on a chassis dynamometer. The vehicle test data indicated CO and NOx could be minimized with a catalyst placed in an intermediate location.

Diesel NOx emissions control utilizing combined Lean NOx Trap (LNT) and so-called passive or in-situ Selective Catalytic Reduction (SCR) catalyst technologies (i.e. with reductant species generated by the LNT) has been the subject of several previous papers from our laboratory [ 1 - 2 ]. The present study focuses on hydrocarbon (HC) emissions control via the same LNT+SCR catalyst technology under FTP driving conditions. HC emissions control can be as challenging as NOx control under both current and future federal and California/Green State emission standards. However, as with NOx control, the combined LNT+SCR approach offers advantages for HC emission control over LNT-only aftertreatment. The incremental conversion obtained with the SCR catalyst is shown, both on the basis of vehicle and laboratory tests, to result primarily from HC adsorbed on the SCR catalyst during rich LNT purges that reacts during subsequent lean engine operation.

Internal combustion (IC) engines fueled by hydrogen are among the most efficient means of converting chemical energy to mechanical work. The exhaust has near-zero carbon-based emissions, and the engines can be operated in a manner in which pollutants are minimal. In addition, in automotive applications, hydrogen engines have the potential for efficiencies higher than fuel cells.[1] In addition, hydrogen engines are likely to have a small increase in engine costs compared to conventionally fueled engines. However, there are challenges to using hydrogen in IC engines. In particular, efficient combustion of hydrogen in engines produces nitrogen oxides (NOx) that generally cannot be treated with conventional three-way catalysts. This work presents the results of experiments which consider changes in direct injection hydrogen engine design to improve engine performance, consisting primarily of engine efficiency and NOx emissions.

Selective catalytic reduction (SCR) of nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.

Natural luminosity (NL) and chemiluminescence (CL) imaging diagnostics are employed to investigate fuel-property effects on mixing-controlled combustion, using select research fuels-a #2 ultra-low sulfur emissions-certification diesel fuel (CF) and four of the Fuels for Advanced Combustion Engines (FACE) diesel fuels (F1, F2, F6, and F8)-that varied in cetane number (CN), distillation characteristics, and aromatic content. The experiments were performed in a single-cylinder heavy-duty optical compression-ignition (CI) engine at two injection pressures, three dilution levels, and constant start-of-combustion timing. If the experimental results are analyzed only in the context of the FACE fuel design parameters, CN had the largest effect on emissions and efficiency.

Robust on-board diagnosis of emission catalyst performance requires the development of artificially damaged "threshold" catalysts that accurately mimic the performance of damaged catalysts in customer use. The threshold catalysts are used by emissions calibrators to determine fore-aft exhaust oxygen sensor responses that indicate catalyst failure. Rather than rely on traditional trial-and-error processes to generate threshold catalysts, we have used a DFSS (Design For Six-Sigma) approach that explores, at a research level, the relationship between oxygen storage capacity (OSC) of the catalyst (i.e., the fundamental property dictating the response of the aft oxygen sensor) and key process input variables: high-temperature exposure, phosphorus poisoning, and catalyst "recovery."

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.

In 1999, the first generation NOx sensor from NGK Spark Plug, Co., Ltd. was commercialized for use in gasoline LNT NOx after-treatment systems [ 1 ]. Since then, as emissions regulations and OBD requirements have become more stringent, the demand for a high-accuracy NOx sensor with fast light-off has increased, particularly for diesel after-treatment systems. To meet such market demands, NGK Spark Plug, Co., Ltd. has developed, in collaboration with Ford Motor Company, a second generation NOx sensor.

Lean NOx traps are being extensively examined (Ref. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12) because they can be efficiently used to reduce the NOx emissions from port fuel injected and direct fuel injected spark ignited gasoline engines. A lean NOx trap (LNT) stores NOx during lean A/F engine operation. However, its storage capacity is limited and the LNT must be regenerated periodically by subjecting the LNT to momentary rich A/F operation for several seconds. The regeneration process releases the NOx that is chemically bonded to the washcoat and subsequently reduces it to N2 and O2. Fuel that contains a non-zero amount of sulfur will contaminate an LNT by significantly reducing its NOx storage capacity. Therefore, except for the case of a zero level of sulfur in the fuel, the LNT must be desulfated on a periodic basis. The desulfation process requires that the temperature of the LNT be raised to a temperature of about 650°C for several minutes.

Controlled Auto-Ignition (CAI) combustion has been achieved in a production type 4-stroke multi-cylinder gasoline engine. The engine was based on a Ford 1.7L Zetec-SE 16V engine with a compression ratio of 10.3, using substantially standard components modified only in design dimensions to control the gas exchange process in order to significantly increase the trapped residuals. The engine was also equipped with Variable Cam Timing (VCT) on both the intake and exhaust camshafts. It was found that the largely increased trapped residuals alone were sufficient to achieve CAI in this engine and with VCT, a range of loads between 0.5 and 4 bar BMEP and engine speeds between 1000 and 3500 rpm were mapped for CAI fuel consumption and exhaust emissions. The measured CAI results were compared with those of Spark Ignition (SI) combustion in the same engine but with standard camshafts at the same speeds and loads.

A simulated diesel exhaust is treated with a nonthermal plasma discharge under steady state conditions. The plasma effluent is then passed through a sodium zeolite-Y (NaY) catalyst followed by a platinum oxidation catalyst. Detailed FTIR measurements of gas composition are taken before, between, and after the treatment stages. The plasma discharge causes oxidation of NO primarily to NO2, with methyl nitrate and nitric acid byproducts. At the same time, HC is partially oxidized, creating species such as formaldehyde, acetaldehyde, CO and other partial oxidation products. When this mixture passes over the NaY catalyst, part of the NOx is reduced to N2, with the remainder primarily in the form of NO. Methyl nitrate decomposes to form methanol and NOx, and nitric acid is consumed. There is little HC conversion on this catalyst. Small quantities of HCN and N2O are formed. When the mixture then passes over the platinum catalyst, further NOx conversion occurs.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

We present here a phenomenological analysis of a cascade of two-step discharge-catalyst reactors. That is, each step of the cascade consists of a discharge reactor in series with a catalyst bed. These reactors are intended for use in the reduction of tailpipe emission of NOx from diesel engines. The discharge oxidizes NO to NO2, and partially oxidizes HC. The NO2 then reacts on the catalyst bed with hydrocarbons and partially oxidized HCs and is reduced to N2. The cascade may be essential because the best catalysts for this purpose that we have also convert significant fractions of the NO2 back to NO. As we show, reprocessing the gas may not only be necessary, but may also result in energy savings and increased device reliability.

The purpose of this paper is to make a preliminary assessment of the potential toxicity of compounds that might be emitted from diesel vehicles using urea/SCR technology. The use of urea as a reductant in the removal of NOx from the exhaust of diesel-powered vehicles has the potential to emit at least seven thermal decomposition products and unreacted urea from the tail-pipe. These compounds include: urea, ammonia, cyanate ion, biuret, cyanuric acid, ammelide, ammeline, and melamine. The toxicity data base for these compounds, in general, is poor. In addition, there have been few, if any, studies examining the inhalation route of exposure - the most likely route of exposure for people from vehicle exhaust. The measurement and identification of these compounds from the exhaust of urea/SCR- equipped vehicles is needed to prioritize the kinds of health effects studies required to understand the toxicity of these compounds.

As part of the P2000 hydrogen fueled internal combustion engine (H2ICE) vehicle program, an engine dynamometer research project was conducted in order to systematically investigate the unique hydrogen related combustion characteristics cited in the literature. These characteristics include pre-ignition, NOx emissions formation and control, volumetric efficiency of gaseous fuel injection and related power density, thermal efficiency, and combustion control. To undertake this study, several dedicated, hydrogen-fueled spark ignition engines (compression ratios: 10, 12.5, 14.5 and 15.3:1) were designed and built. Engine dynamometer development testing was conducted at the Ford Research Laboratory and the University of California at Riverside. This engine dynamometer work also provided the mapping data and control strategy needed to develop the engine in the P2000 vehicle.