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Technical Paper

Extent of Oxidation of Hydrocarbons Desorbing from the Lubricant Oil Layer in Spark-ignition Engines

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.
Technical Paper

Auto-Oil Program Phase II Heavy Hydrocarbon Study: Analysis of Engine-Out Hydrocarbon Emissions Data

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.
Technical Paper

Novel Experiment on In-Cylinder Desorption of Fuel from the Oil Layer

A technique has been developed to measure the desorption and subsequent oxidation of fuel in the oil layer by spiking the oil with liquid fuel and firing the engine on gaseous fuel or motoring with air. Experiments suggest that fuel desorption is not diffusion limited above 50 °C and indicated that approximately two to four percent of the cylinder oil layer is fresh oil from the sump. The increase in hydrocarbon emissions is of the order of 100 ppmC1 per 1% liquid fuel introduced into the fresh oil in a methane fired engine at mid-speed and light load conditions. Calculations indicate that fuel desorbing from oil is much more likely to produce hydrocarbon emissions than fuel emerging from crevices.
Technical Paper

Auto-Oil Program Phase II Heavy Hydrocarbon Study: Fuel Species Oxidation Chemistry and Its Relationship to the Auto-Oil Data

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.
Technical Paper

Effect of Engine Operating Parameters on Hydrocarbon Oxidation in the Exhaust Port and Runner of a Spark-Ignited Engine

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.
Technical Paper

Chemical Kinetic Modeling of the Oxidation of Unburned Hydrocarbons

The chemistry of unburned hydrocarbon oxidation in SI engine exhaust was modeled as a function of temperature and concentration of unburned gas for lean and rich mixtures. Detailed chemical kinetic mechanisms were used to model isothermal reactions of unburned fuel/air mixture in an environment of burned gases at atmospheric pressure. Simulations were performed using five pure fuels (methane, ethane, propane, n-butane and toluene) for which chemical kinetic mechanisms and steady state hydrocarbon (HC) emissions data were available. A correlation is seen between reaction rates and HC emissions for different fuels. Calculated relative amounts of intermediate oxidation products are shown to be consistent with experimental measurements.
Technical Paper

Autoignition of Alcohols and Ethers in a Rapid Compression Machine

The autoignition characteristics of methanol, ethanol and MTBE (methyl tert-butyl ether) have been investigated in a rapid compression machine at pressures in the range 20-40 atm and temperatures within 750-1000 K. All three oxygenated fuels tested show higher autoignition temperatures than paraffins, a trend consistent with the high octane number of these fuels. The autoignition delay time for methanol was slightly lower than predicted values using reported reaction mechanisms. However, the experimental and measured values for the activation energy are in very good agreement around 44 kcal/mol. The measured activation energy for ethanol autoignition is in good agreement with previous shock tube results (31 kcal/mol), although ignition times predicted by the shock tube correlation are a factor of three lower than the measured values. The measured activation energy for MTBE, 41.4 kcal/mol, was significantly higher than the value previously observed in shock tubes (28.1 kcal/mol).
Technical Paper

Flame Kernel Development in a Methanol Fueled Engine

The combustion behavior in a modem 4-valve engine using a broad range of methanol/gasoline fuel mixtures was studied. The initial flame development was examined by using a spark plug fiber optics probe. Approximately, the kernel expansion speed, Sg, is relatively unchanged from M0 to M40; jumps by ∼30% from M40 to M60; and then remains roughly constant from M60 to M100. Statistics of the IMEP indicate that at a lean idle condition the combustion rate and robustness correlate with Sg: a higher value of Sg gives better combustion. Thus M60-M100 fuels give better idle combustion behavior than the M0-M40 fuels.
Technical Paper

Real World Performance of an Onboard Gasoline/Ethanol Separation System to Enable Knock Suppression Using an Octane-On-Demand Fuel System

Higher compression ratio and turbocharging, with engine downsizing can enable significant gains in fuel economy but require engine operating conditions that cause engine knock under high load. Engine knock can be avoided by supplying higher-octane fuel under such high load conditions. This study builds on previous MIT papers investigating Octane-On-Demand (OOD) to enable a higher efficiency, higher-boost higher compression-ratio engine. The high-octane fuel for OOD can be obtained through On-Board-Separation (OBS) of alcohol blended gasoline. Fuel from the primary fuel tank filled with commercially available gasoline that contains 10% by volume ethanol (E10) is separated by an organic membrane pervaporation process that produces a 30 to 90% ethanol fuel blend for use when high octane is needed. In addition to previous work, this paper combines modeling of the OBS system with passenger car and medium-duty truck fuel consumption and octane requirements for various driving cycles.
Technical Paper

Alcohol Fueled Heavy Duty Vehicles Using Clean, High Efficiency Engines

Non-petroleum based liquid fuels are essential for reducing oil dependence and greenhouse gas generation. Increased substitution of alcohol fuel for petroleum based fuels could be achieved by 1) use in high efficiency spark ignition engines that are employed for heavy duty as well as light duty operation and 2) use of methanol as well as ethanol. Methanol is the liquid fuel that is most efficiently produced from thermo-chemical gasification of coal, natural gas, waste or biomass. Ethanol can also be produced by this process but at lower efficiency and higher cost. Coal derived methanol is in limited initial use as a transportation fuel in China. Methanol could potentially be produced from natural gas at an economically competitive fuel costs, and with essentially the same greenhouse gas impact as gasoline. Waste derived methanol could also be an affordable low carbon fuel.
Technical Paper

Using Mass Spectrometry to Detect Ethanol and Acetaldehyde Emissions from a Direct Injection Spark Ignition Engine Operating on Ethanol/Gasoline Blends

Ethanol and acetaldehyde emissions from a direct ignition spark ignition were measured using mass spectrometry. Previous methods focused on eliminating or minimizing interference from exhaust species with identical atomic mass and fragment ions created in ionization process. This paper describes a new technique which exploits the fragment ions from ethanol and acetaldehyde. A survey of mass spectra of all major species of exhaust gas was conducted. It was found that ethanol contributes most ions in mass number 31 and that no other gas species produces ions at this mass number. Acetaldehyde detection suffers more interference. Nevertheless, it was estimated that detection at mass number 43 is possible with 10% error from 2-methylbutane. This new technique was validated in an engine experiment. By running the engine with pure gasoline and E85, the validity of the technique can be checked.
Technical Paper

A New Approach to Ethanol Utilization: High Efficiency and Low NOx in an Engine Operating on Simulated Reformed Ethanol

The use of hydrogen as a fuel supplement for lean-burn engines at higher compression ratios has been studied extensively in recent years, with good promise of performance and efficiency gains. With the advances in reformer technology, the use of a gaseous fuel stock, comprising of substantially higher fractions of hydrogen and other flammable reformate species, could provide additional improvements. This paper presents the performance and emission characteristics of a gas mixture of equal volumes of hydrogen, CO, and methane. It has recently been reported that this gas mixture can be produced by reforming of ethanol at comparatively low temperature, around 300C. Experiments were performed on a 1.8-liter passenger-car Nissan engine modified for single-cylinder operation. Special pistons were made so that compression ratios ranging from CR= 9.5 to 17 could be used. The lean limit was extended beyond twice stoichiometric (up to lambda=2.2).
Technical Paper

Fuel Effects on HCCI Operation in a Spark Assisted Direct Injection Gasoline Engine

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.
Technical Paper

Effect of Operating Conditions and Fuel Type on Crevice HC Emissions: Model Results and Comparison with Experiments

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.
Technical Paper

Detailed Calculation of Heating, Evaporation, and Reaction Processes of a Thin Liquid Layer of Hydrocarbon Fuel

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.
Technical Paper

Effects of Ethanol Evaporative Cooling on Particulate Number Emissions in GDI Engines

The spark ignition engine particulate number (PN) emissions have been correlated to a particulate matter index (PMI) in the literature. The PMI value addresses the fuel effect on PN emission through the individual fuel species reactivity and vapor pressure. The latter quantity is used to account for the propensity of the non-volatile fuel components to survive to the later part of the combustion event as wall liquid films, which serve as sources for particulate emission. The PMI, however, does not encompass the suppression of vaporization by the evaporative cooling of fuel components, such as ethanol, that have high latent heat of vaporization. This paper assesses this evaporative cooling effect on PN emissions by measurements in a GDI engine operating with a base gasoline which does not contain oxygenate, with a blend of the gasoline and ethanol, and with a blend of the gasoline, ethanol, and a hydrocarbon additive so that the blend has the same PMI as the original gasoline.
Journal Article

Particulate Matter Emissions from a Direct Injection Spark Ignition Engine under Cold Fast Idle Conditions for Ethanol-Gasoline Blends

The engine out particular matter number (PN) distributions at engine coolant temperature (ECT) of 0° C to 40° C for ethanol/ gasoline blends (E0 to E85) have been measured for a direct-injection spark ignition engine under cold fast idle condition. For E10 to E85, PN increases modestly when the ECT is lowered. The distributions, however, are insensitive to the ethanol content of the fuel. The PN for E0 is substantially higher than the gasohol fuels at ECT below 20° C. The total PN values (obtained from integrating the PN distribution from 15 to 350 run) are approximately the same for all fuels (E0 to E85) when ECT is above 20° C. When ECT is decreased below 20° C, the total PN values for E10 to E85 increase modestly, and they are insensitive to the ethanol content. For E0, however, the total PN increases substantially. This sharp change in PN from E0 to E10 is confirmed by running the tests with E2.5 and E5. The midpoint of the transition occurs at approximately E5.
Journal Article

Assessment of Gasoline Direct Injection Engine Cold Start Particulate Emission Sources

The gasoline direct injection (GDI) engine particulate emission sources are assessed under cold start conditions: the fast idle and speed/load combinations representative of the 1st acceleration in the US FTP. The focus is on the accumulation mode particle number (PN) emission. The sources are non-fuel, combustion of the premixed charge, and liquid fuel film. The non-fuel emissions are measured by operating the engine with premixed methane/air or hydrogen/air. Then the PN level is substantially lower than what is obtained with normal GDI operation; thus non-fuel contribution to PN is small. When operating with stoichiometric premixed gasoline/air, the PN level is comparable to the non-fuel level; thus premixed-stoichiometric mixture combustion does not significantly generate particulates. For fuel rich premixed gasoline/air, PN increases dramatically when lambda is less than 0.7 to 0.8.
Technical Paper

Flex Fuel Gasoline-Alcohol Engines For Near Zero Emissions Plug-In Hybrid Long Haul Trucks

Internal combustion engines for plug-in hybrid heavy duty trucks, especially long haul trucks, can play an important role in facilitating use of battery power. Power from a low carbon electricity source could thereby be employed without an unattractive vehicle cost increase or range limitation. The ideal engine should be powered by a widely available affordable liquid fuel, should minimize air pollutant emissions, and should provide lower greenhouse gas emissions. Diesel engines fall short in meeting these objectives, especially because of high NOx emissions. In this paper we describe features of flex fuel alcohol enhanced gasoline engines in series hybrid powertrains where the engines have the same or greater efficiency of diesel engines while also having 90% lower NOx emissions. Ethanol or methanol is employed to increase knock resistance and provide improved combustion.
Journal Article

Effects of Ethanol Content on Gasohol PFI Engine Wide-Open-Throttle Operation

The NOx emission and knock characteristics of a PFI engine operating on ethanol/gasoline mixtures were assessed at 1500 and 2000 rpm with λ =1 under Wide-Open-Throttle condition. There was no significant charge cooling due to fuel evaporation. The decrease in NOx emission and exhaust temperature could be explained by the change in adiabatic flame temperature of the mixture. The fuel knock resistance improved significantly with the gasohol so that ignition could be timed at a value much closer or at MBT timing. Changing from 0% to 100% ethanol in the fuel, this combustion phasing improvement led to a 20% increase in NIMEP and 8 percentage points in fuel conversion efficiency at 1500 rpm. At 2000 rpm, where knocking was less severe, the improvement was about half (10% increase in NIMEP and 4 percentage points in fuel conversion efficiency).