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To meet increasingly stringent diesel engine emission regulations, diesel engines are required to use ultra-low sulfur diesel (ULSD) and are equipped with advanced aftertreatment systems. Cu-SSZ-13 zeolite catalysts are widely used as selective catalytic reduction (SCR) catalysts due to their high NOx reduction and excellent hydrothermal stability. However, active Cu sites of Cu-SSZ-13 catalysts can be poisoned by exposure to engine exhaust sulfur species. This poison effect can be mitigated with the use of ULSD and high temperature exposure from engine operation. On the other hand, ULSD is still not universally available where regulations require it, and vehicles may inadvertently operate with high sulfur diesel fuel (HSD) in some locations. The high concentration of exhaust sulfur species resulting from HSD combustion may rapidly poison the Cu-SSZ-13 SCR catalyst. In this study, the catalytic performance of a sulfur poisoned Cu-SSZ-13 SCR catalyst is analyzed.

Comparisons have been made between dual-fuel (80% port-injection gasoline and 20% direct-injection diesel by mass) Highly Premixed Charge Combustion (HPCC) and blended-fuel (80% gasoline and 20% diesel) Low Temperature Combustion (LTC) modes on a 1-L single-cylinder test engine. In the HPCC mode, both early-injection (E-HPCC) and late-injection (L-HPCC) of diesel have been used. The comparisons have been conducted with a fixed fuel injection rate of 50 mg/cycle at 1500 rpm, and with the combustion phasing fixed (by adjusting the injection timing) so that the 50% heat release point (CA50) is at 8° ATDC. The rapid heat release process of LTC leads to the highest maximum pressure rise rate (MPRR). A two-peak heat release process is observed in L-HPCC, resulting in a lower MPRR. The heat release rate and MPRR values for the E-HPCC are comparable to the L-HPCC values. The EHPCC mode provides the lowest NOX emission. The soot emissions for all three modes are low.

Diesel engines have been identified as contributing to more than half of the transport sectors black carbon (BC) emissions in the US. This large contribution to atmospheric BC concentrations has raised concern about source specific emission rates, including off-highway engines. The European Union has recently implemented more stringent particulate regulations in the form of particle number via the Particle Measurement Programme (PMP) methodology. The PMP method counts the non-volatile fraction of particulate matter (PM) above 23 nm and below 2.5 μm via a condensation particle counter. This study evaluates a surrogate black carbon method which uses the PMP particle count method with a correlation factor to the BC fraction. The transient capable Magee Scientific Aethalometer (AE-33) 880 nm wavelength channel was used to determine the BC fraction.

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).

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.

A comparative analysis was made on the emissions from a 2004 and a 2007 heavy-duty diesel engine to determine how new engine and emissions technologies have affected the chemical compounds found in the exhaust gases. Representative samples were collected from a source dilution sampling system and analyzed for both criteria and unregulated gaseous and particulate emissions. Results have shown that the 2007 regulations compliant engine and emissions technology not only reduced the specifically regulated exhaust pollutants, but also significantly reduced the majority of unregulated chemical species. It is believed that these reductions were achieved through the use of engine optimization, aftertreatment system integration, and ultra-low sulfur diesel fuel.

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.

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.

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 NOx emissions during the crank-start and cold fast-idle phases of a GDI engine are analyzed in detail. The NOx emissions of the first 3 firing cycles are studied under a wide set of parameters including the mass of fuel injected, start of injection, and ignition timing. The results show a strong dependence of the NOx emissions with injection timing; they are significantly reduced as the mixture is stratified. The impact of different valve timings on crank-start NOx emissions was analyzed. Late intake and early exhaust timings show similar potential for NOx reduction; 26-30% lower than the baseline. The combined strategy, resulting in a large symmetric negative valve overlap, shows the greatest reduction; 59% lower than the baseline. The cold fast-idle NOx emissions were studied under different equivalence ratios, injection strategies, combustion phasing, and valve timings. Slightly lean air-fuel mixtures result in a significant reduction of NOx.

While metal fiber filters have successfully shown a high degree of particle retention functionality for various sizes of diesel engines with a low pressure drop and a relatively high filtration efficiency, little is known about the effects of lubricant-derived ash on the fiber filter systems. Sintered metal fiber filters (SMF-DPF), when used downstream from a diesel engine, effectively trap and oxidize diesel particulate matter via an electrically heated regeneration process where a specific voltage and current are applied to the sintered alloy fibers. In this manner the filter media essentially acts as a resistive heater to generate temperatures high enough to oxidize the carbonaceous particulate matter, which is typically in excess of 600°C.

Ash, primarily derived from diesel engine lubricants, accumulates in diesel particulate filters directly affecting the filter's pressure drop sensitivity to soot accumulation, thus impacting regeneration frequency and fuel economy. After approximately 33,000 miles of equivalent on-road aging, ash comprises more than half of the material accumulated in a typical cordierite filter. Ash accumulation reduces the effective filtration area, resulting in higher local soot loads toward the front of the filter. At a typical ash cleaning interval of 150,000 miles, ash more than doubles the filter's pressure drop sensitivity to soot, in addition to raising the pressure drop level itself. In order to evaluate the effects of lubricant-derived ash on DPF pressure drop performance, a novel accelerated ash loading system was employed to generate the ash and load the DPFs under carefully-controlled exhaust conditions.

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.

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.

Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.

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.

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.

Studies have shown that there are a significant number of chemical species present in engine exhaust particulate matter emissions. Additionally, the majority of current world-wide regulatory methods for measuring engine particulate emissions are gravimetrically based. As modern engines considerably reduce particulate mass emissions, these methods become less stable and begin to display higher levels of measurement uncertainty. In this study, a characterization of mass emissions from three heavy-duty diesel engines, with a range of particulate emission levels, was made in order to gain a better understanding of the variability and uncertainty associated with common mass measurement methods, as well as how well these methods compare with each other. Two gravimetric mass measurement methods and a reconstructed mass method were analyzed as part of the present study.