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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.

Ammonia oxidation (AMOX) catalysts are critical parts of most diesel aftertreatment systems around the world. These catalysts are positioned downstream of selective catalytic reduction (SCR) catalysts and remove unreacted NH3 that passes through the SCR catalyst. In many configurations, the AMOX catalyst is situated after a diesel oxidation catalyst and catalyzed diesel particulate filter that oxidize CO and hydrocarbons. However, in Euro V and proposed Tier 4 final aftertreatment architectures there is no upstream oxidation catalyst. In this study, the impact of hydrocarbons is evaluated on two different types of AMOX catalysts. One has dual washcoat layers-SCR washcoat on top of PGM washcoat-and the other has only a PGM washcoat layer. Results are presented for NH3 and hydrocarbon oxidation, NOx and N2O selectivity, and hydrocarbon storage. The AMOX findings are rationalized in terms of their impact on the individual oxidation and SCR functions.

Lean-burn natural gas (NG) engines are used world-wide for both stationary power generation and mobile applications ranging from passenger cars to Class 8 line-haul trucks. With the recent introduction of hydraulic fracturing gas extraction technology and increasing availability of natural gas, these engines are receiving more attention. However, the reduction of unburned hydrocarbon emissions from lean-burn NG and dual-fuel (diesel and natural gas) engines is particularly challenging due to the stability of the predominant short-chain alkane species released (e.g., methane, ethane, and propane). Supported Pd-based oxidation catalysts are generally considered the most active materials for the complete oxidation of low molecular weight alkanes at temperatures typical of lean-burn NG exhaust. However, these catalysts rapidly degrade under realistic exhaust conditions with high water vapor concentrations and traces of sulfur.

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.

Diesel particulate filters are designed to reduce the mass emissions of diesel particulate matter and have been proven to be effective in this respect. Not much is known, however, about their effects on other unregulated chemical species. This study utilized source dilution sampling techniques to evaluate the effects of a catalyzed diesel particulate filter on a wide spectrum of chemical emissions from a heavy-duty diesel engine. The species analyzed included both criteria and unregulated compounds such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), inorganic ions, trace metallic compounds, elemental and organic carbon (EC and OC), polycyclic aromatic hydrocarbons (PAHs), and other organic compounds. Results showed a significant reduction for the emissions of PM mass, CO, HC, metals, EC, OC, and PAHs.

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.

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.

Natural gas-powered engines are widely used due to their low fuel cost and in general their lower emissions than conventional diesel engines. In order to comply with emissions regulations, an aftertreatment system is utilized to treat exhaust from natural gas engines. Stoichiometric burn natural gas engines use three-way catalyst (TWC) technology to simultaneously remove NOx, CO, and hydrocarbon (HC). Removal of methane, one of the major HC emissions from natural gas engines, is difficult due to its high stability, posing a challenge for existing TWC technologies. In this work, degreened (DG), standard bench cycle (SBC)-aged TWC catalysts and a DG Pd-based oxidation catalyst (OC) were evaluated and compared under a variety of lean/rich gas cycling conditions, simulating stoichiometric natural gas engine emissions.

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.

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.

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.

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.

Regulations on methane emissions from lean-burn natural gas (NG) and lean-burn dual fuel (natural gas and diesel) engines are becoming more stringent due to methane’s strong greenhouse effect. Palladium-based oxidation catalysts are typically used for methane reduction due to their relative high reactivity under lean conditions. However, the catalytic activity of these catalysts is inhibited by the water vapor in exhaust and decreases over time from exposure to trace amounts of sulfur. The reduction of deactivated catalysts in a net rich environment is known to be able to regenerate the catalyst. In this work, a multicycle methane light-off & extinction test protocol was first developed to probe the catalyst reactivity and stability under simulated exhaust conditions. Then, the effect of two different regeneration gas compositions, denoted as regen-A and regen-B, was evaluated on a degreened catalyst and a catalyst previously tested on a natural gas engine.

Natural gas powered vehicles are attractive in certain applications due to their lower emissions in general than conventional diesel engines and the low cost of natural gas. For stoichiometric natural gas engines, the aftertreatment system typically consists only of a three-way catalyst (TWC). However, increasingly stringent NOx and methane regulations challenge current TWC technologies. In this work, a catalyst reactor system with variable lean/rich switching capability was developed for evaluating TWCs for stoichiometric natural gas engines. The effect of varying frequency and duty-cycle during lean/rich gas switching experiments was measured with a hot-wire anemometer (HWA) due to its high sensitivity to gas thermal properties. A theoretical reactor gas dispersion model was then developed and validated with the HWA measurements. The model is capable of predicting the actual lean/rich gas exposure to the TWC under different testing conditions.

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.

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.