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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.

In order to understand better the operation of spark-ignition engines during the warm-up period, a computer model had been developed which simulates the thermal processes of the engine. This model is based on lumped thermal capacitance methods for the major engine components, as well as the exhaust system. Coolant and oil flows, and their respective heat transfer rates are modeled, as well as friction heat generation relations. Piston-liner heat transfer is calculated based on a thermal resistance method, which includes the effects of piston and ring material and design, oil film thickness, and piston-liner crevice. Piston/liner crevice changes are calculated based on thermal expansion rates and are used in conjunction with a crevice-region unburned hydrocarbon model to predict the contribution to emissions from this source.

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.

The Leaner Lifted-Flame Combustion (LLFC) strategy offers a possible alternative to low temperature combustion or other globally lean, premixed operation strategies to reduce soot directly in the flame, while maintaining mixing-controlled combustion. Adjustments to fuel properties, especially fuel oxygenation, have been reported to have potentially beneficial effects for LLFC applications. Six fuels were selected or blended based on cetane number, oxygen content, molecular structure, and the presence of an aromatic hydrocarbon. The experiments compared different fuel blends made of n-hexadecane, n-dodecane, methyl decanoate, tri-propylene glycol monomethyl ether (TPGME), as well as m-xylene. Several optical diagnostics have been used simultaneously to monitor the ignition, combustion and soot formation/oxidation processes from spray flames in a constant-volume combustion vessel.

A dynamometer-mounted four-cylinder Saturn engine was used to accumulate combustion chamber deposits (CCD), using an additized fuel. During each deposit accumulation test, the HC emissions were continuously measured. The deposit thickness at the center of the piston was measured at the beginning of each day. After the 50 and 35-hour tests, HC emissions were measured with isooctane, benzene, toluene, and xylene, with the deposited engine, and again after the deposits had been cleaned from the engine. The HC emissions showed a rapid rise in the first 10 to 15 hours and stabilization after about 25 hours of deposit accumulation. The HC increase due to CCD accumulation accounted for 10 to 20% of the total engine-out HC emissions from the deposit build-up fuel and 10 to 30% from benzene, isooctane, toluene, and xylene, making CCDs a significant HC emissions source from this engine. The HC emissions stabilized long before the deposit thickness.

A research program designed to measure the contribution from fuel absorption in the thin layer of oil, lubricating the cylinder liner, to the total and speciated HC emissions from a spark ignition engine has been performed. The logic of the experiment design was to test the oil layer mechanism via variations in the oil layer thickness (through the lubricant formulations), solubility of the fuel components in the lubricants, and variations in the crankcase gas phase HC concentration (through crankcase purging). A set of preliminary experiments were carried out to determine the solubility and diffusivity of the fuel components in the individual lubricants. Engine tests showed similar HC emissions among the tested lubricants. No consistent increase was observed with oil viscosity (oil film thickness), contrary to what would be expected if fuel-oil absorption was contributing significantly to engine-out HC. Similarly, no effect of crankcase purging could be observed.

A single-cylinder, spark-ignited engine was run on a certification test gasoline to saturate the oil in the sump with fuel through exposure to blow-by gas. The sump volume was large relative to production engines making its absorption-desorption time constant long relative to the experimental time. The engine was motored at 1500 RPM, 90° C coolant and oil temperature, and 0.43 bar MAP without fuel flow. Exhaust HC concentrations were measured by on-line FID and GC analysis. The total motoring HC emissions were 150 ppmC1; the HC species distribution was heavily weighted to the low-volatility components in the gasoline. No high volatility components were visible. The engine was then fired on isooctane fuel at the above conditions, producing a total engine-out HC emission of 2300 ppmC1 for Φ = 1.0 and MBT spark timing.

Until now no results have been available regarding the composition of evaporative emissions in a SHED test. In particular, for alcohol containing fuels, it is important to assess the relative percentage of alcohols and hydrocarbons in view of their different environmental impacts. This paper presents the results of a study conducted to determine the composition of the emissions from a number of multilayer coextruded plastic fuel tanks soaked in IE10 and CM15 test fuels. These emissions were analyzed for composition using a gas chromatography analytical method which employs a vapor trap and desorb sampling technique. In the case of CM15, methanol was found to account for as much as 50% of the overall evaporative emissions. This speciation method also allows estimation of how leakage and permeation contribute separately to the overall emissions.

The occurrence of flash boiling in the fuel spray of a Port Fuel Injected (PFI) spark ignition engine has been observed and photographed during normal automotive vehicle operating conditions. The flash boiling of the PFI spray has a dramatic affect on the fuel spray characteristics such as droplet size and spray cone angle which can affect engine transient response, intake valve temperature and possibly hydrocarbon emissions. A new method of correlating the spray behavior using the equilibrium vapor/liquid (V/L) volume ratio of the fuel at the measured fuel temperature and manifold pressure is introduced.

The presence of liquid fuel inside the engine cylinder is believed to be a strong contributor to the high levels of hydrocarbon emissions from spark ignition (SI) engines during the warm-up period. Quantifying and determining the fate of the liquid fuel that enters the cylinder is the first step in understanding the process of emissions formation. This work uses planar laser induced fluorescence (PLIF) to visualize the liquid fuel present in the cylinder. The fluorescing compounds in indolene, and mixtures of iso-octane with dopants of different boiling points (acetone and 3-pentanone) were used to trace the behavior of different volatility components. Images were taken of three different planes through the engine intersecting the intake valve region. A closed valve fuel injection strategy was used, as this is the strategy most commonly used in practice. Background subtraction and masking were both performed to reduce the effect of any spurious fluorescence.

Measurements of particulate matter (PM) from spark ignition (SI) engine exhaust using dilution tunnels will become more prevalent as emission standards are tightened. Hence, a study of the dilution process was undertaken in order to understand how various dilution related parameters affect the accuracy with which PM sizes and concentrations can be determined. A SI and a compression ignition (CI) engine were separately used to examine parameters of the dilution process; the present work discusses the results in the context of SI exhaust dilution. A Scanning Mobility Particle Sizer (SMPS) was used to measure the size distribution, number density, and volume fraction of PM. Temperature measurements in the exhaust pipe and dilution tunnel reveal the degree of mixing between exhaust and dilution air, the effect of flowrate on heat transfer from undiluted and diluted exhaust to the environment, and the minimum permissible dilution ratio for a maximum sample temperature of 52°C.

A lean-rich hydrothermal aging was used to study the deactivation of Cu-zeolite SCR catalyst that has enhanced stability. Impact of DOC upstream on the SCR catalyst during the lean-rich aging was also investigated. The LR hydrothermal aging was conducted with the presence of hydrocarbon, CO and H₂ at different O₂ levels. It was found that the SCR catalyst was active for the oxidation of CO, H₂ and hydrocarbon, resulting in significant exotherm across the catalyst. In addition to hydrothermal aging, reductive aging, especially the presence of H₂ in the aging gas stream without O₂ presence during the L-R aging, might also contribute to the Cu/zeolite SCR catalyst deactivation. The impacts of DOC upstream on Cu/zeolite SCR catalysts depended on the aging temperatures. At lower aging temperature, the uncompleted oxidation of hydrocarbon and CO on the DOC might cause steam reforming and water-gas shift reactions on the DOC to form reductive gas stream.

Hydrogen can be readily used in spark-ignition engines as a clean alternative to fossil fuels. However, a larger burning velocity and a shorter quenching distance for hydrogen as compared with hydrocarbons bring a larger cooling loss from burning gas to the combustion-chamber wall. Because of the large cooling loss, the thermal efficiency of a hydrogen-fueled engine is sometimes lower than that of a conventionally fueled engine. Therefore, the reduction of the cooling loss is very important for improving the thermal efficiency in hydrogen-combustion engines. On the other hand, the direct-injection stratified charge can suppress knocking in spark-ignition engines at near stoichiometric overall mixture conditions. Because this is attributed to a leaner end gas, the stratification can lead to a lowered temperature of burning gas around the wall and a reduced cooling loss.

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.

This paper presents results from an experimental programme researching the in-cylinder conditions necessary to obtain homogenous CAI (or HCCI) combustion in a 4-stroke engine. The fuels under investigation include three blends of Unleaded Gasoline, a 95 RON Primary Reference Fuel, Methanol, and Ethanol. This work concentrates on establishing the CAI operating range with regard to Air/Fuel ratio and Exhaust Gas Re-circulation and their effect on the ignition timing, combustion rate and variability, Indicated thermal efficiency, and engine-out emissions such as NOx. Detailed maps are presented, defining how each of the measured variables changes over the entire CAI region. Results indicate that the alcohols have significantly higher tolerance to dilution than the hydrocarbon fuels tested. Also, variations in Gasoline blend have little effect on any of the combustion parameters measured.

Particulate and manganese mass emissions have been measured as a function of mileage for four Escort and four Explorer vehicles using 1) MMT (Methylcyclopentadienyl Manganese Tricarbonyl) added to the gasoline at 1/32 g Mn/gal and 2) gasoline without MMT. The MMT was used in half of the fleet starting at 5,000 miles. The vehicles were driven on public roads at an average speed of 54 mph to accumulate mileage. This report describes the particulate and manganese emissions, plus emissions of four air toxics at 5,000, 20,000, 55,000, 85,000 and 105,000 miles. Four non-regulated emissions were measured and their average values for vehicles without MMT were 0.6 mg/mi for formaldehyde, 0.7 mg/mi for 1,3-butadiene, 9 mg/mi for benzene and 12 mg/mi for toluene. Corresponding values for MMT-fueled vehicles were between 1.5 and 2.4 times higher.

Measurements of oxygen storage capacity (OSC) and HC conversion efficiency for 17 catalysts were carried out in the laboratory. All catalysts with steady state HC efficiency below 90% were found to have roughly equivalent and very low capacities to store oxygen. However, catalyst oxygen storage capacity was seen to rise sharply with HC conversion efficiency in excess of 90 percent. These results parallel the trends which are observed between rear HEGO/EGO indexes for OBD-II catalyst monitoring and HC conversion efficiency. In addition, temperature programed reduction (TPR) was found to lend insight into the relationship between catalyst OSC and HC conversion efficiency by providing a qualitative understanding of the mechanisms by which OSC deteriorates. TPR profiles showed that most of the usable oxygen storage is derived from surface ceria which is interacted with precious metals.

The fuel effects on HCCI operation in a spark assisted direct injection gasoline engine are assessed. The low load limit has been extended with a pilot fuel injection during the negative valve overlap (NVO) period. The fuel matrix consists of hydrocarbon fuels and various ethanol blends and a butanol blend, plus fuels with added ignition improvers. The hydrocarbon fuels and the butanol blend do not significantly alter the high or the low limits of operation. The HCCI operation appears to be controlled more by the thermal environment than by the fuel properties. For E85, the engine behavior depends on the extent that the heat release from the pilot injected fuel in the NVO period compensates for the evaporative cooling of the fuel.

An experimental study was performed in a firing SI engine at conditions representative of the warmup phase of operation in which liquid gasoline films were established at various locations in the combustion chamber and the resulting impact on hydrocarbon emissions was assessed. Unique about this study was that it combined, in a firing engine environment, direct visual observation of the liquid fuel films, measurements of the temperatures these films were subjected to, and the determination from gas analyzers of burned and unburned fuel quantities exiting the combustion chamber - all with cycle-level resolution or better. A means of deducing the exhaust hydrocarbon emissions that were due to the liquid fuel films in the combustion chamber was developed. An increase in exhaust hydrocarbon emissions was always observed with liquid fuel films present in the combustion chamber.