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A fuel volatility model based on the major species present in the fuel has been formulated. The model accurately predicts the ASTM distillation curves and Reid Vapor Pressure for hydrocarbon fuels. The model may be used to assess the fuel effects on the extent of evaporation and the vapor composition in the mixture preparation process.

This paper provides an overview of spark-ignition engine unburned hydrocarbon emissions mechanisms, and then uses this framework to relate measured engine-out hydrocarbon emission levels to the processes within the engine from which they result. Typically, spark-ignition engine-out HC levels are 1.5 to 2 percent of the gasoline fuel flow into the engine; about half this amount is unburned fuel and half is partially reacted fuel components. The different mechanisms by which hydrocarbons in the gasoline escape burning during the normal engine combustion process are described and approximately quantified. The in-cylinder oxidation of these HC during the expansion and exhaust processes, the fraction which exit the cylinder, and the fraction oxidized in the exhaust port and manifold are also estimated.

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.

The direct injection spark-ignition engine is the only internal combustion engine with the potential to equal the efficiency of the diesel and to tolerate a wide range of fuel types and fuel qualities without deterioration of performance. However, this engine has low combustion efficiency and excessive hydrocarbon emissions when operating at light load. In this paper, potential sources of hydrocarbon emissions during light load operation are postulated and analyzed. The placement of fuel away from the primary combustion process in conjunction with a lack of secondary burnup are isolated as important hydrocarbon emissions mechanisms. Analyses show that increasing cylinder gas temperatures can improve secondary burnup of fuel which would reduce hydrocarbon emissions. Practical means to achieve this include higher compression ratio and use of ceramic parts in the combustion chamber.

The engine-out (EO) total and speciated hydrocarbon emissions data from the Auto-Oil Program Phase II Heavy Hydrocarbon Study had been analyzed. The methodology was to first investigate the stabilized EO emissions (Bag 2) of a specific vehicle (Vehicle 04B, a 1989 Model Year Ford Taurus); then the vehicle-to-vehicle differences in Bag2 emissions were considered. Finally, the differences in the Bag2 and the starting/warm-up EO emissions (Bag1) were examined. The speciated emissions may be interpreted as a “feed-through” part due to the unreacted fuel species, and an “offset” part due to the decomposition products. The significant non-fuel emitted species were methane and the olefins. The HC emissions for vehicles with different total emissions were similar in species composition. For both the total and speciated emissions, there was no substantial difference between the Bag1 and Bag2 values for Vehicle 04B.

The oxidation chemistry of paraffins, aromatics, olefins and MTBE were examined. Detailed chemical kinetics calculations were carried out for oxidation of these compounds in the engine cycle. The oxidation rates are very sensitive to temperature. At temperatures of over 1400 K (depending on the fuel), all the hydrocarbons are essentially oxidized for typical residence time in the engine. Based on the kinetics calculations, a threshold temperature is defined for the conversion of the fuel species to CO, CO2, H2O and partially oxidized products. The difference in the survival fraction between aromatics and non-aromatics is attributed to the higher threshold temperature of the aromatics.

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.

An experimental study was conducted on a direct-injection stratified-charge (DISC) engine incorporating a combustion process similar to the Texaco Controlled Combustion System and operated with gasoline. Analysis of the injected fuel flow and the heat release showed that the combustion process was characterized by three distinct phases: fuel injection and distribution around the piston bowl, flame propagation through the stratified fuel-air mixture, and mixing-controlled burn-out with the heat-release rate proportional to the amount of unburned fuel in the combustion chamber. This characterization was consistent with previous visualization studies conducted on rapid-compression machines with similar configurations. Experiments with varied injection timing, spark plug location, and spark timing showed that the combustion timing relative to injection was critical to the hydrocarbon emissions from the engine.

NO2 is an effective soot oxidizer operating at lower temperatures than O2. The effect of pure NO2 on soot oxidation was evaluated and compared with the gas treated by plasma, which initially consisted of NO, O2, and hydrocarbons. The cutout of a commercial DPF was used and the pressure difference across the DPF was monitored for an hour. The concentration of NO/NO2, CO, CO2 at the outlet of the DPF was measured as a function of time. CO and CO2 concentration was measured periodically by gas chromatography. The experiment was performed at 230, 250, 300, 350°C. When NO2 only was used as an oxidizing agent, there was a close relationship between the decrease of the pressure difference across the DPF, the CO and CO2 concentration at the outlet of the DPF, and the back conversion of NO2 to NO.

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 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.

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.

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.

Effect of various hydrocarbons on the plasma DeNOx process in simulated diesel engine operating conditions is investigated experimentally and theoretically. This paper shows the results of an extensive series of experiments on the NOx conversion effect of various hydrocarbons (methane, ethene, propene, propane) in the plasma. The effects of energy density, temperature, and the initial concentrations of hydrocarbon and oxygen are discussed and the results for each hydrocarbon are compared with one another. The energy required to convert one NO molecule is measured 13.8eV, 16.1eV, 23.2eV, 45.6eV for propene, ethene, propane, methane, respectively when energy density of 25.4J/L is delivered to the mixture of 10% O2, base N2 with 440ppm NO and 500ppm hydrocarbon at 473K, while it is 143.2eV without hydrocarbon. The best NOx conversion effect of propene among the mentioned hydrocarbons is due to the highest reaction rates of propene with O and OH.

An experimental study was performed to investigate the effects of various intake charge motion control valves (CMCVs) on mixture preparation, combustion, and hydrocarbon (HC) emissions during the cold start-up process of a port fuel injected spark ignition (SI) engine. Different charge motions were produced by three differently shaped plates in the CMCV device, each of which blocked off 75% of the engine's intake ports. Time-resolved HC, CO and CO2 concentrations were measured at the exhaust port exit in order to achieve cycle-by-cycle engine-out HC mass and in-cylinder air/fuel ratio. Combustion characteristics were examined through a thermodynamic burn rate analysis. Cold-fluid steady state experiments were carried out with the CMCV open and closed. Enhanced charge motion with the CMCV closed was found to shorten the combustion duration, which caused the location of 50% mass fraction burned (MFB) to occur up to 5° CA earlier for the same spark timing.

Experiments were conducted to determine the effects of substantial spark retard on combustion, hydrocarbon (HC) emissions, and exhaust temperature, under cold engine conditions. A single-cylinder research engine was operated at 20° C fluid temperatures for various spark timings and relative air/fuel ratios. Combustion stability was observed to decrease as the phasing of the 50% mass fraction burned (MFB) occurred later in the expansion stroke. A thermodynamic burn rate analysis indicated combustion was complete at exhaust valve opening with -20° before top dead center (BTDC) spark timings. Chemical and thermal energy of the exhaust gas was tracked from cylinder-exit to the exhaust runner. Time-resolved HC concentrations measured in the port and runner were mass weighted to obtain an exhaust HC mass flow rate. Results were compared to time averaged well downstream HC levels.

Two features to facilitate chemical reactions at low temperature, non-thermal plasma and the weak dependency of photocatalyst on temperature, have been exploited by many researchers to effectively decompose hydrocarbon emissions emitted until the light-off of a three-way catalyst in spark ignition engines. To develop a realizable emissions reduction reactor, as part of such effort, this study investigates for the three model gases, propylene, n-butane and acetylene: 1) the conversion efficiency of the emissions reduction reactor, which utilizes the effect of dissociation, ionization-by-collision of the non-thermal plasma and the photocatalytic effect of TiO2, and 2) the concentrations of the products such as acetaldehyde, acetic acid, polymerized hydrocarbons and NO2. The operating parameters to obtain the plasma energy density ranging from 7.8 to 908 J/L were varied.

The flow into and out of the piston top-land crevice of a spark-ignition engine has been studied, using a square-cross-section single-cylinder engine with two parallel quartz glass walls which permit optical access to the entire cylinder volume. Schlieren short-time exposure photographs and high speed movies were used to define the essential features of this flow. The top-land crevice and the regions behind and between the rings consist of volumes connected through the ring gaps. A system model of volumes and orifices was therefore developed and used to predict the flow into and out of the crevice regions between the piston, piston rings and cylinder wall.

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.

High levels of hydrocarbon emissions during light load operation keep the direct injection stratified charge engine from commercial application. Previous analytical work has identified several possible hydrocarbon emissions mechanisms which can result from poor in-cylinder fuel distribution. Poor fuel distribution can be caused by erratic fuel injection. Experiments conducted on a single cylinder DISC engine show a dramatic increase in the cycle to cycle variation in injection characteristics as engine load decreases. This is accompanied by an increase in cycle to cycle variation in combustion behavior suggesting that degradation in combustion results from the degradation in the quality of the injection event. Examination of combustion and injection characteristics on a cycle by cycle basis shows that, at light load, IMEP and heat release do not correlate with the amount of fuel injected into the cylinder.