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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.

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.

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.

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 purpose of this work was to develop an understanding of how liquid fuel transported into the cylinder of a port-fuel-injected gasoline-fueled SI engine contributes to hydrocarbon (HC) emissions. To simulate the liquid fuel flow from the valve seat region into the cylinder, a specially designed fuel probe was developed and used to inject controlled amounts of liquid fuel onto the port wall close to the valve seat. By operating the engine on pre-vaporized Indolene, and injecting a small amount of liquid fuel close to the valve seat while the intake valve was open, we examined the effects of liquid fuel entering the cylinder at different circumferential locations around the valve seat. Similar experiments were also carried out with closed valve injection of liquid fuel at the valve seat to assess the effects of residual blowback, and of evaporation from the intake valve and port surfaces.

A one-dimensional model has been developed for the species and energy transfer over a thin (0.1-0.5 mm) layer of liquid fuel present on the wall of a spark-ignition engine. Time-varying boundary conditions during compression and flame passage were used to determine the rate of methanol vaporization and oxidation over a mid-speed, mid-load cycle, as a function of wall temperature. The heat of vaporization and the boiling point of the fuel were varied about a baseline to determine the effect of these characteristics, at a fixed operating point and lean conditions (ϕ = 0.9). The calculations show that the evaporation of fuels from layers on cold walls starts during flame passage, peaking a few milliseconds later, and continuing through the exhaust phase.

A one-dimensional model for crevice HC post-flame oxidation is used to calculate and understand the effect of operating parameters and fuel type (propane and isooctane) on the extent of crevice hydrocarbon and the product distribution in the post flame environment. The calculations show that the main parameters controlling oxidation are: bulk burned gas temperatures, wall temperatures, turbulent diffusivity, and fuel oxidation rates. Calculated extents of oxidation agree well with experimental values, and the sensitivities to operating conditions (wall temperatures, equivalence ratio, fuel type) are reasonably well captured. Whereas the bulk gas temperatures largely determine the extent of oxidation, the hydrocarbon product distribution is not very much affected by the burned gas temperatures, but mostly by diffusion rates. Uncertainties in both turbulent diffusion rates as well as in mechanisms are an important factor limiting the predictive capabilities of the model.

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 cold-start partial oxidation (POX) system was integrated with a modern flexible fuel engine to assess its impact on cold-start performance and emissions. The POX reactor, a small combustion device operating fuel rich, converts liquid fuel into gaseous fuel species (reformate). The reformate from the reactor, when mixed with combustion air, replaces or supplements the standard fuel consumed during an engine start. This prototype integrated cold-start system has successfully reduced emissions from a cold-start on fuel grade ethanol (E95) at 5°C. The integrated POX system reduced the time-averaged hydrocarbon (HC) and carbon monoxide (CO) emissions by 80 and 40 percent, respectively. Starts on E95 reformate were achieved in less than 10 seconds at temperatures as low as -20°C.

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.

About 50-90 percent of the hydrocarbons that escape combustion during flame passage in spark-ignition engine operation are oxidized in the cylinder before leaving the system. The process involves the transport of unreacted fuel from cold walls towards the hotter burned gas regions and subsequent reaction. In order to understand controlling factors in the process, a transient one-dimensional reactive-diffusive model has been formulated for simulating the oxidation processes taking place in the reactive layer between hot burned gases and cold unreacted air/fuel mixture, with initial and boundary conditions provided by the emergence of hydrocarbons from the piston top land crevice. Energy and species conservation equations are solved for the entire process, using a detailed chemical kinetic mechanism for propane.

A sampling system was developed to measure the evolution of the speciated hydrocarbon emissions from a single-cylinder SI engine in a simulated starting and warm-up procedure. A sequence of exhaust samples was drawn and stored for gas chromatograph analysis. The individual sampling aperture was set at 0.13 s which corresponds to ∼ 1 cycle at 900 rpm. The positions of the apertures (in time) were controlled by a computer and were spaced appropriately to capture the warm-up process. The time resolution was of the order of 1 to 2 cycles (at 900 rpm). Results for four different fuels are reported: n-pentane/iso-octane mixture at volume ratio of 20/80 to study the effect of a light fuel component in the mixture; n-decane/iso-octane mixture at 10/90 to study the effect of a heavy fuel component in the mixture; m-xylene and iso-octane at 25/75 to study the effect of an aromatics in the mixture; and a calibration gasoline.

A method to collect and speciate the components of gasoline absorbed in the lubricant oil using gas chromatography has been developed. Samples were collected continuously from the piston skirt, baffle and sump in a Saturn engine. A long (18 hours) test was performed to determine the build up of hydrocarbons in the sump, and a shorter (25 min) test was performed to determine the build up of hydrocarbons in the piston skirt and baffle during engine warm-up. The first experiment showed that the total hydrocarbon concentration in the sump oil reached a steady state of about 1.35% mass fraction after 11 hours of engine operation. The relative concentration of individual fuel hydrocarbon species absorbed in the oil increases exponentially with boiling point. Most of the identified species in the oil consist of the heavy end aromatics. Similar compositions but lower concentrations were found for samples collected from the piston skirt during engine warm-up.

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke.

In order to understand how unburned hydrocarbons emerge from SI engines and, in particular, how non-fuel hydrocarbons are formed and oxidized, a new gas sampling technique has been developed. A sampling unit, based on a combination of techniques used in the Fast Flame Ionization Detector (FFID) and wall-mounted sampling valves, was designed and built to capture a sample of exhaust gas during a specific period of the exhaust process and from a specific location within the exhaust port. The sampling unit consists of a transfer tube with one end in the exhaust port and the other connected to a three-way valve that leads, on one side, to a FFID and, on the other, to a vacuum chamber with a high-speed solenoid valve. Exhaust gas, drawn by the pressure drop into the vacuum chamber, impinges on the face of the solenoid valve and flows radially outward.

The effect of engine operating parameters (speed, spark timing, and fuel-air equivalence ratio [Φ]) on hydrocarbon (HC) oxidation within the cylinder and exhaust system is examined using propane or isooctane fuel. Quench gas (CO2) is introduced at two locations in the exhaust system (exhaust valve or port exit) to stop the oxidation process. Increasing the speed from 1500 to 2500 RPM at MBT spark timing decreases the total, cylinder-exit HC emissions by ∼50% while oxidation in the exhaust system remains at 40% for both fuels. For propane fuel at 1500 rpm, increasing Φ from 0.9 (fuel lean) to 1.1 (fuel rich) reduces oxidation in the exhaust system from 42% to 26%; at 2500 RPM, exhaust system oxidation decreases from 40% to approximately 0% for Φ = 0.9 and 1.1, respectively. Retarded spark increases oxidation in the cylinder and exhaust system for both fuels. Decreases in total HC emissions are accompanied by increased olefinic content and atmospheric reactivity.

A model has been developed which predicts engine-out hydrocarbon (HC) emissions for spark-ignition engines. The model consists of a set of scaling laws that describe the individual processes that contribute to HC emissions. The model inputs are the critical engine design and operating variables. This set of individual process scaling relations was then calibrated using production spark-ignition engine data at a fixed light-load operating point. The data base consisted of engine-out HC emissions from two-valve and four-valve engine designs with variations in spark timing, valve timing, coolant temperature, crevice volume, and EGR, for five different engines. The model was calibrated separately for the three different engines to accommodate differences in engine design details and to determine the relative magnitudes of each of the major sources. A good fit to this database was obtained.

An analysis method for characterizing fuel behavior during spark-ignition engine starting has been developed and applied to several sets of start-up data. The data sets were acquired from modern production vehicles during room temperature engine start-up. Two different engines, two control schemes, and two engine temperatures (cold and hot) were investigated. A cycle-by-cycle mass balance for the fuel was used to compare the amount of fuel injected with the amount burned or exhausted as unburned hydrocarbons. The difference was measured as “fuel unaccounted for”. The calculation for the amount of fuel burned used an energy release analysis of the cylinder pressure data. The results include an overview of starting behavior and a fuel accounting for each data set Overall, starting occurred quickly with combustion quality, manifold pressure, and engine speed beginning to stabilize by the seventh cycle, on average.