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In this study, high-temperature deactivation of a fully-formulated lean NOx trap (LNT) is investigated with an accelerated aging protocol where accelerated aging is accomplished by rapid temperature cycling and by higher temperatures. Thermal aging is carried out in a bench-flow reactor at nominal temperatures of 700, 800, 900, and 1000°C using an aging cycle consisting of a 130s lean-phase and a 50s rich-phase. After a prescribed number of lean/rich aging cycles, the NOx conversion of the aged LNT is evaluated at 200, 300, and 400°C. The NOx performance is obtained at a GHSV of 30,000 h−1 using an evaluation cycle consisting of a 60s lean-phase and 5s rich-phase. The effects of aging on the LNT washcoat are determined with EPMA, XRD, STEM/EDS, and BET. Aging at 700 and 800°C has a minimal effect on LNT performance and material properties.

The effects of variable compression ratio (CR) and fuel composition on thermal efficiency were investigated in a homogeneous charge compression ignition (HCCI) engine using blends of n-heptane and toluene with research octane numbers (RON) of 0 to 90. Experiments were conducted by performing CR sweeps at multiple intake temperatures using both unthrottled operation, and constant Φ conditions by throttling to compensate for varying air density. It was found that CR is effective at changing and controlling the HCCI combustion phasing midpoint, denoted here as CA 50. Thermal efficiency was a strong function of CA 50, with overly advanced CA 50 leading to efficiency decreases. Increases in CR at a constant CA 50 for a given fuel composition did, in most cases, increase efficiency, but the relationship was weaker than the dependence of efficiency on CA 50.

In order to meet common fuel specifications such as cetane number and volatility, a refinery must blend a number of refinery stocks derived from various process units in the refinery. Fuel chemistry can be significantly altered in meeting fuel specifications. Additionally, fuel specifications are seldom changed in isolation, and the drive to meet one specification may alter other specifications. Homogeneous charge compression ignition (HCCI) engines depend on the kinetic behavior of a fuel to achieve reliable ignition and are expected to be more dependent on fuel specifications and chemistry than today's conventional engines. Regression analysis can help in determining the underlying relationships between fuel specifications, chemistry, and engine performance. Principal Component Analysis (PCA) is used as an adjunct to regression analysis in this work, because of its ability to deal with co-linear variables and potential to uncover ‘hidden’ relationships between the variables.

The effect of biodiesel content on homogeneous charge compression ignition (HCCI) engine performance has been investigated both experimentally and by computer simulation. Combustion experiments were performed in a single cylinder HCCI engine using blends of soy biodiesel in ultra low sulfur diesel, with concentrations ranging from 0 to 50 vol% and equivalence ratios (Φ) from 0.38 to 0.48. Data from the engine tests included combustion analysis and exhaust composition analysis with standard gaseous emissions equipment. The engine utilized a custom port fuel injection strategy to provide highly premixed charges of fuel and air, making it possible to compare the results with single zone chemical kinetics simulations that were performed using CHEMKIN III, with a reaction set including 670 species and over 3000 reactions.

In this research, small, single cylinder engines have been used to simulate larger engines in the areas of aftertreatment, combustion, and fuel formulation effects. The use of small engines reduces overall research cost and allows more rapid experiments to be run. Because component costs are lower, it is also possible to investigate more variations and to sacrifice components for materials characterization and for subsequent experiments. Using small engines in this way is very successful in some cases. In other cases, limitations of the engines influence the results and need to be accounted for in the experimental design and data analysis. Some of the results achieved or limitations found may be of interest to the small engine market, and this paper is offered as a summary of the authors' research in these areas. Research is being conducted in two areas. First, small engines are being used to study the rapid aging and poisoning of exhaust aftertreatment catalysts.

On a gasoline engine platform, homogeneous charge compression ignition (HCCI) holds the promise of improved fuel economy and greatly reduced engine-out NOx emissions, without an increase in particulate matter emissions. In this investigation, a variable compression ratio (CR) engine equipped with a throttle and intake air heating was used to test the robustness of these control parameters to accommodate a series of fuels blended from reference gasoline, straight run refinery naphtha, and ethanol. Higher compression ratios allowed for operation with higher octane fuels, but operation could not be achieved with the reference gasoline, even at the highest compression ratio. Compression ratio and intake heat could be used separately or together to modulate combustion. A lambda of 2 provided optimum fuel efficiency, even though some throttling was necessary to achieve this condition. Ethanol did not appear to assist combustion, although only two ethanol-containing fuels were evaluated.

In the present study, a bench-flow reactor is used to perform lean/rich thermal cycling on model “Ba+K” LNT catalysts at temperatures of 700, 800, 900 and 1000°C using simulated diesel exhaust gases. Deterioration of NOx performance is measured and the deactivation mechanisms of thermally-aged “Ba+K” LNTs are identified using characterization techniques such as TEM, XRD and EPMA. Results indicate that the deterioration is minimal at 700 and 800°C, however, at aging temperatures exceeding 800°C the severity of thermal aging depends on aging temperature as well as number of aging cycles.

As the world market develops for biodiesel fuels, it is likely that a wider variety of biodiesels will become available, both locally and globally, and require engines to operate on a wider variety of fuels than experienced today. At the same time, tighter emissions regulations and a drive for improved fuel economy have focused interest on advanced combustion modes such as HCCI or PCCI, which are known to be more sensitive to fuel properties. This research covers two series of biodiesel fuels. In the first, B20 blends of natural methyl esters derived from palm, coconut, rape, soy, and mustard were evaluated at light load in an HCCI research engine to determine combustion and performance characteristics. These fuels showed performance differences between the biodiesels and the base #2 ULSD fuel, but did not allow separation of chemical effects due to the small number of fuels and correlation of various properties.

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/γ-AI2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation.

To address the growing need for accurate predictions of combustion phasing and emissions for development of advanced engines, a more accurate definition of model fuels and their associated chemical-kinetics mechanisms are necessary. Wide variations in street fuels require a model-fuel blending methodology to allow simulation of fuel-specific characteristics, such as ignition timing, emissions, and fuel vaporization. We present a surrogate-blending technique that serves as a practical modeling tool for determination of surrogate blends specifically tailored to different real-fuel characteristics, with particular focus on model fuels for gasoline engine simulation. We start from a palette of potential model-fuel components that are based on the characteristic chemical classes present in real fuels. From this palette, components are combined into a surrogate-fuel blend to represent a real fuel with specific fuel properties.

The accelerated ash loading of diesel particulate filters (DPFs) with diesel oxidation catalysts (DOCs) mounted upstream by lube-oil derived products was investigated using a single cylinder diesel engine and fuel blended with 5% lube oil. An ash loading protocol is developed which combines soot loading, active soot regeneration, and periodic shutdowns for filter weighing. Active regeneration is accomplished by exhaust injection of diesel fuel, initiated by a backpressure criteria and providing DPF temperatures up to 700°C. In developing this protocol, five DPFs of various combinations of substrates (cordierite, silicon carbide, and mullite) and washcoats (none, low PGM, and high PGM) are used and evaluated. The initial backpressure and rate of backpressure increase with ash varied with each of the DPFs and ash was observed to have an effect on the active soot light-off temperature for the catalyzed DPFs.

Diesel fuels derived from different types of crude oil can exhibit different chemistry while still meeting market requirements and specifications. Oil sands derived fuels typically contain a larger proportion of cycloparaffinic compounds, which result from the cracking and hydrotreating of bitumens in the crude. In the current study, 17 refinery streams consisting of finished fuels and process streams were obtained from a refinery using 100% oil sands derived crude oil. All samples except one met the ULSD standard of 15 ppm sulfur. The samples were characterized for properties and chemistry and run in a simple premixed HCCI engine using intake heating for combustion phasing control. Results indicate that the streams could be equally well characterized by chemistry or properties, and some simple correlations are presented. Cetane number was found to relate mainly to mono-aromatic content and the cycloparaffins did not appear to possess any unique diesel related chemical effects.

While gasoline surrogate development has progressed in the areas of more complex surrogate mixtures and in kinetic modeling tools and mechanism development, it is generally recognized that further development is still needed. This paper represents a small step in supporting this development by providing comparisons between experimental engine data and surrogate-based kinetic models. In our case, the HCCI engine data comes from a port-injected, single-cylinder research engine with intake-air heating for combustion phasing control. Timing sweeps were run at constant fuel rate for three market gasolines and five surrogate mixtures. Modeling was done using the CHEMKIN software with a gasoline mechanism set containing 1440 species and 6572 reactions. Five pure compounds were selected for the surrogate blends and include iso-octane, n-heptane, toluene, methylcyclohexane, and 1-hexene.

The nine CRC fuels for advanced combustion engines (FACE fuels) have been evaluated in a simple, premixed HCCI engine under varying conditions of fuel rate, air-fuel ratio, and intake temperature. Engine performance was found to vary mainly as a function of combustion phasing as affected by fuel cetane and engine control variables. The data was modeled using statistical techniques involving eigenvector representation of the fuel properties and engine control variables, to define engine response and allow optimization across the fuels for best fuel efficiency. In general, the independent manipulation of intake temperature and air-fuel ratio provided some opportunity for improving combustion efficiency of a specific fuel beyond the direct effect of targeting the optimum combustion phasing of the engine (near 5 CAD ATDC).

In this investigation, oil shale crude obtained from the Green River Formation in Colorado using Paraho Direct retorting was mildly hydrotreated and distilled to produce 7 narrow boiling point fuels of equal volumes. The resulting derived cetane numbers ranged between 38.3 and 43.9. Fuel chemistry and bulk properties strongly correlated with boiling point. The fuels were run in a simple HCCI engine to evaluate combustion performance. Each cut exhibited elevated NOx emissions, from 150 to 300ppm higher than conventional ULSD under similar conditions. Engine performance and operating range were additionally dictated by distillation temperatures which are a useful predictor variable for this fuel set. In general, cuts with low boiling point achieved optimal HCCI combustion phasing while higher boiling point cuts suffered a 25% fuel economy decrease, compared to conventional diesel under similar HCCI conditions, and incurred heavy engine deposits.

The poisoning of diesel oxidation catalysts (DOCs) by the engine oil additive zinc dialkyldithiophosphate (ZDDP) is investigated in the present study. A 517cc single-cylinder diesel engine is used to accelerate the phosphorus poisoning of DOCs by artificially increasing the ZDDP consumption to approximately 700 times normal operation by three different methods. These include lube-oil doped fuel, intake manifold, and exhaust manifold injection with lube-oil containing an elevated level of ZDDP. The deactivation of DOCs under these conditions is characterized by a variety of physical and chemical techniques. Surface composition and structure of the poisoned catalysts analyzed with SEM-EDS show differences depending on the method of ZDDP introduction. Exhaust manifold injection produces a zinc phosphate glaze which masks the surface to species diffusion. Fuel and intake manifold injection methods produce chemically absorbed phosphorus on the catalyst washcoat surface.

Knowledge of how fuel chemistry and properties affect engine response is necessary for effective engine control. It may also be possible to tailor fuels to specific combustion modes, engine geometries, or for desired outputs to generate lower emissions and/or higher IMEP and efficiency. Fuel chemistry and properties have different effects on engine performance in CI and HCCI combustion. In this study, experiments were performed using a 517cc Hatz single-cylinder diesel engine and the same engine converted to run in HCCI mode, both equipped with advanced combustion analysis equipment. Engine performance results were modeled statistically with respect to fuel properties, operating parameters, and engine type to determine the extent to which fuel characteristics influence engine response, and how the response differs between the two combustion modes. Experiments were performed using 16 fuels: ULSD, 9 FACE diesel fuels, and 6 P20 blends of unprocessed plant oils.

We report experimental observations of cyclic combustion variability during the transition between propagating flame combustion and homogeneous charge compression ignition (HCCI) in a single-cylinder, stoichiometrically fueled, spark-assisted gasoline engine. The level of internal EGR was controlled with variable valve actuation (VVA), and HCCI combustion was achieved at high levels of internal EGR using the VVA system. Spark-ignition was used for conventional combustion and was optionally available during HCCI. The transition region between purely propagating combustion and HCCI was mapped at multiple engine speeds and loads by incrementally adjusting the internal EGR level and capturing data for 2800 sequential cycles. These measurements revealed a complex sequence of high COV, cyclic combustion variations when operating between the propagating flame and HCCI limits.

Widespread implementation of homogeneous charge compression ignition (HCCI) engines is presently hindered by stability, control, and load range issues. Although the operable HCCI speed/load range is expanding, it is likely that the initial HCCI engines will rely on conventional combustion for part of the operating cycle. In the present study, we have investigated the role of fuel properties and chemistry on the operation of a spark-assisted gasoline HCCI engine. The engine employed is a single cylinder, 500 cc, port fuel injected research engine, operating near lambda = 1.0 and equipped with hydraulic variable valve actuation. HCCI is initiated by early exhaust valve closing to retain exhaust in the cylinder, thereby increasing the cylinder gas temperature. This is also referred to as a ‘negative overlap’ strategy.

The effects of cetane number (CN) on homogeneous charge compression ignition (HCCI) performance and emissions were investigated in a single cylinder engine using intake air temperature for control. Blends of the diesel secondary reference fuels for cetane rating were used to obtain a CN range from 19 to 76. Sweeps of intake air temperature at a constant fueling were performed. Low CN fuels needed to be operated at higher intake temperatures than high CN fuels to achieve ignition. As the intake air temperature was reduced for a given fuel, the combustion phasing was retarded, and each fuel passed through a phasing point of maximum indicated mean effective pressure (IMEP). Early combustion phasing was required for the high CN fuels to prevent misfire, whereas the maximum IMEP for the lowest CN fuel occurred at a phasing 10 crank angle degrees (CAD) later.