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Engine-out HC emissions from a PFI spark ignition engine were measured using a gas chromatograph and a flame ionization detector (FID). Two port fuel injectors were used respectively for ethanol and gasoline so that the delivered fuel was comprised of 0, 25, 50, 75 and 100% (by volume) of ethanol. Tests were run at 1.5, 3.8 and 7.5 bar NIMEP and two speeds (1500 and 2500 rpm). The main species identified with pure gasoline were partial reaction products (e.g. methane and ethyne) and aromatics, whereas with ethanol/gasoline mixtures, substantial amounts of ethanol and acetaldehyde were detected. Indeed, using pure ethanol, 74% of total HC moles were oxygenates. In addition, the molar ratio of ethanol to acetaldehyde was determined to be 5.5 to 1. The amount (as mole fraction of total HC moles) of exhaust aromatics decreased linearly with increasing ethanol in the fuel, while oxygenate species correspondingly increased.

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.

To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.

Effects of methyl ester biodiesel fuel blends on NOx emissions are studied experimentally and analytically. A precisely controlled single cylinder diesel engine experiment was conducted to determine the impact of a 20% blend of soy methyl ester biodiesel (B20) on NOx emissions. The data were then used to calibrate KIVA chemical kinetics models which were used to determine how the biodiesel blend affects NOx production during the combustion process. In addition, the impact on the engine control system of the lower specific energy content of biodiesel was determined. Both factors, combustion and controls, must be taken into account when determining the net NOx effect of biodiesel compared to conventional diesel fuel. Because the magnitude and even direction of NOx effect changes with engine load, the NOx effect associated with burning biodiesel blends over a duty cycle depends on the duty cycle average power and fuel cetane number.

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.

The use of biodiesel requires the development of proper quantification procedures for biodiesel content in blends and in lubricants (fuel dilution in oil). Although the ester carbonyl stretch at 1746 wavenumbers (cm-1) is the most prominent band in the IR spectrum of biodiesel, it is difficult to use for quantification purposes due to a severe fluctuation of absorption strength from sample to sample, even at the same biodiesel content. We have demonstrated that the ester carbonyl fluctuation is not caused by variation in the ester alkyl chain length; but is most likely caused by the degree of hydrogen bonding of the ester functional group with water in the sample. Water molecules can form complexes with the ester compound affecting the strength of the ester carbonyl band. The impact of water on quantification of the biodiesel content of blends was significant, even for B100 samples that met the proposed ASTM D6751 water limit of 500 ppm by D6304 (Karl Fischer Methdod).

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.

Gaseous and particle emissions from a gasoline direct injection (GDI) and a port fuel injection (PFI) vehicle were measured at various ambient temperatures (22°C, -7°C, -18°C). These vehicles were driven over the U.S. Federal Test Procedure 75 (FTP-75) and US06 Supplemental Federal Test Procedure (US06) on Tier 2 certification gasoline (E0) and 10% by volume ethanol (E10). Emissions were analyzed to determine the impact of ambient temperature on exhaust emissions over different driving conditions. Measurements on the GDI vehicle with a gasoline particulate filter (GPF) installed were also made to evaluate the GPF particle filtration efficiency at cold ambient temperatures. The GDI vehicle was found to have better fuel economy than the PFI vehicle at all test conditions. Reduction in ambient temperature increased the fuel consumption for both vehicles, with a much larger impact on the cold-start FTP-75 drive cycle observed than for the hot-start US06 drive cycle.

In the early years of antifreeze/coolants (1920s & 30s) glycerin saw some usage, but because of higher cost and weaker freeze point depression, it was not competitive with ethylene glycol. Glycerin is a by-product of the manufacture of biodiesel (fatty acid methyl esters) made by reacting natural vegetable or animal fats with methanol. Biodiesel fuel is becoming increasingly important and is expected to gain a large market share in the next several years. Regular diesel fuels blended with 2%, 5%, and 20% biodiesel are now commercially available. The large amount of glycerin generated from high volume usage of biodiesel fuel has resulted in this chemical becoming cost competitive with the glycols currently used in engine coolants. For this reason, and lower toxicity comparable to that of propylene glycol, glycerin deserves to be reconsidered as a base for antifreeze/coolant.

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.

Heat rejection, liner temperature, exhaust valve seat temperature, and head gasket temperature data were recorded during a full load torque sweep of a compression ignition engine when fueled by No. 2 diesel and an ethanol/diesel fuel blend containing 10% ethanol by volume. Heat balances were calculated for engine operation at various load-speed combinations. The results of this study indicated that a greater than expected volume of E-diesel was required to operate the compression ignition engine at the same torque-speed compared to No. 2 diesel. More E-diesel fuel was required due to lower brake thermal efficiencies for E-diesel. Other than exhaust seat temperatures, there were no appreciable differences in component temperatures measured throughout the engine or the results of the heat balances calculated for the No. 2 diesel and E-diesel fuels.

Cummins Westport Inc. (CWI) released for production the latest version of its C8.3G natural gas engine, the C Gas Plus, in July 2001. This engine has increased ratings for horsepower and torque, a full-authority engine controller, wide tolerance to natural gas fuel (the minimum methane number is 65), and improved diagnostics capability. The C Gas Plus also meets the California Air Resources Board optional low-NOx (2.0 g/bhp-h) emission standard for automotive and urban buses. Two pre-production C Gas Plus engines were operated in a Viking Freight fleet for 12 months as part of the U.S. Department of Energy's Fuels Utilization Program. In-use exhaust emissions, fuel economy, and fuel cost were collected and compared with similar 1997 Cummins C8.3 diesel tractors. CWI and the West Virginia University developed an ad-hoc test cycle to simulate the Viking Freight fleet duty cycle from in-service data collected with data loggers.

Oxygen storage capacity (OSC) is one of the most critical characteristics of a three-way catalyst (TWC) and is closely related to the catalyst aging and performance. In this study, a dynamic OSC model involving two oxygen storage sites with distinct kinetics was developed. The dual-site OSC model was validated on a bench reactor and a natural gas engine. The model was capable of predicting temperature dependence on OSC with H2, CO and CH4 as reductants. Also, the effects of oxygen concentration and space velocity on the amount of OSC were captured by the model. The validated OSC model was applied to simulate lean breakthrough phenomena with varied space velocities and oxygen concentrations. It is found that OSC during lean breakthrough is not a constant for a particular TWC catalyst and is dependent on space velocity and oxygen concentration. Specifically, breakthrough time exhibits a non-linear, inverse correlation to oxygen flux.

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.

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.

The aging impact on oxygen storage capacity (OSC) and catalyst performance was investigated on one degreened and one aged (hydrothermally aged at 955 °C for 50 h) commercial three-way catalyst (TWC) by experiments and modeling. The difference of OSC between the degreened and aged TWCs was dependent on catalyst temperature. The largest difference was found at 600 °C, at which the amount of OSC decreased by 45.5%. Catalyst performance was evaluated through lightoff tests at two simulated engine exhaust conditions (lean and rich) on a micro-reactor. The aging impact on the catalyst performance was different under lean and rich environments and investigated separately. At the lean condition, oxidation of CO and C3H6 was significantly suppressed while oxidation of C3H8 was relatively less degraded. At the rich condition, the inhibition effect was more pronounced on the aged TWC and inhibiting hydrocarbon species from C3H6 partial oxidation can survive at temperatures up to 450 °C.

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.

A 1.9L turbocharged direct-injection engine representing a model year 1998-2003 Volkswagen vehicle, equipped with the OEM diesel oxidation catalyst (DOC) and exhaust gas recirculation (EGR), was tested on an eddy-current engine dynamometer with a critical flow venturi-constant volume sampling system (CFV-CVS). The engine was operated over three steady-state modes: 1600 rev/min at 54 Nm; 1800 rev/min at 81 Nm; and 2000 rev/min at 98 Nm. Commercially available ultra-low sulfur diesel fuel (≺15 ppm S) was splash-blended with fatty acid methyl ester biodiesels derived from three different feedstocks: canola, soy, and tallow/waste fry oil. Test blend levels included: 0%, 2%, 5%, 20%, 50%, and 100% biodiesel for each feedstock.

Adoption of hydro-processed esters and fatty acid biojet fuels is a critical component for the sustainability of the aviation industry. Aviation biofuels reduce pollution and provide alternatives to conventional fossil fuels. A study of the impacts of biofuels on emissions from a T56 turbo-prop engine was undertaken as a joint effort among several departments of the Government of Canada. In this study, particulate (including particle number and black carbon (BC) mass) and regulated gaseous emissions (CO2, CO, NO, NO2, THC) were characterized with the engine operating on conventional F-34 jet fuel and jet fuel blended with camelina-based hydro-processed biojet fuel (C-HEFA) by 50% in volume. Emissions characterization, conducted after 20-hour ground engine durability tests, showed immediate significant reductions in particle number and BC mass when the engine was operated on the C-HEFA blend.

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).