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Biodiesel (i.e., mono-alkyl esters of long chain fatty acids derived from vegetable oils and animal fats) is a renewable diesel fuel providing life-cycle greenhouse gas emission reductions relative to petroleum-derived diesel. With the expectation that there would be widespread use of biodiesel as a substitute for ultra-low sulfur diesel (ULSD), there have been many studies looking into the effects of biodiesel on engine and aftertreatment, particularly its compatibility to the current aftertreatment technologies. The objective of this study was to generate experimental data to measure the effectiveness of a current technology diesel oxidation catalysts (DOC) to oxidize soy-based biodiesel at various blend levels with ULSD. Biodiesel blends from 0 to 100% were evaluated on an engine using a conventional DOC.

Biodiesel is a promising alternative to traditional diesel fuel due to its similar combustion properties to diesel and lower carbon emissions on a well-to-wheel basis. However, combusting biodiesel still generates hydrocarbon (HC), CO, NOx and particulate matter (PM) emissions, similar to those from traditional diesel fuel usage. Therefore, aftertreatment systems will be required to reduce these emissions to meet increasingly stringent emission regulations to minimize the impact to the environment. Diesel oxidation catalysts (DOC) are widely used in modern aftertreatment systems to convert unburned HC and CO, to partially convert NO to NO2 to enhance downstream selective catalytic reaction (SCR) catalyst efficiency via fast SCR and to periodically clean-up DPF via controlled soot oxidation. In this work, we focus on the performance difference between biodiesel and diesel over a commercial DOC catalyst to identify the knowledge gap during the transition from diesel fuel to biodiesel.

The steam reforming of CH4 plays a crucial role in the high-temperature activity of natural gas three-way catalysts. Despite existing reports on sulfur inhibition in CH4 steam reforming, there is a limited understanding of sulfur storage and removal dynamics under various lambda conditions. In this study, we utilize a 4-Mode sulfur testing approach to elucidate the dynamics of sulfur storage and removal and their impact on three-way catalyst performance. We also investigate the influence of sulfur on CH4 steam reforming by analyzing CH4 conversions under dithering, rich, and lean reactor conditions. In the 4-Mode sulfur test, saturating the TWC with sulfur at low temperatures emerges as the primary cause of significant three-way catalyst performance degradation. After undergoing a deSOx treatment at 600 °C, NOx conversions were fully restored, while CH4 conversions did not fully recover.

Low carbon emissions policies for the transportation sector have recently driven more interest in using low net-carbon fuels, including biodiesel. An internal combustion engine (ICE) can operate effectively using biodiesel while achieving lower engine-out emissions, such as soot, mostly thanks to oxygenate content in biodiesel. This study selected a heavy-duty (HD) single-cylinder engine (SCE) platform to test biodiesel fuel blends with 20% and 100% biodiesel content by volume, referred to as B20, and B100. Test conditions include a parametric study of exhaust gas recirculating (EGR), and the start of injection (SOI) performed at low and high engine load operating points. In-cylinder pressure and engine-out emissions (NOX and soot) measurements were collected to compare diesel and biodiesel fuels.

Alternative fuels such as methanol can significantly reduce greenhouse gas (GHG) emissions when used in internal combustion engines (ICEs). This study characterized the combustion of methanol, methanol/diesel, and methanol/renewable diesel numerically. Numerical findings were also compared with engine experiments using a single-cylinder engine (SCE). The engine was operated under a dual-fuel combustion mode: methanol was fumigated at the intake port, and diesel was injected inside the cylinder. The characteristic of ignition delay trend as methanol concentration increased is being described at low temperature (low engine load) and high temperature (high engine load) conditions.

As an alternative fuel, renewable diesel (RD) could improve the performance of conventional internal combustion engines (ICE) because of its difference in fuel properties. With almost no aromatic content in the fuel, RD produces less soot emissions than diesel. The higher cetane number (CN) of RD also promotes ignition of the fuel, which is critical, especially under low load, and low reactivity conditions. This study tested RD fuel in a heavy-duty single-cylinder engine (SCE) under compression-ignition (CI) operation. Test condition includes low and high load points with change in exhaust gas recirculation (EGR) and start of injection (SOI). Measurements and analysis are provided to study combustion and emissions, including particulate matters (PM) mass and particle number (PN). It was found that while the combustion of RD and diesel are very similar, PM and PN emissions of RD were reduced substantially compared to diesel.

The prediction accuracy of a three-way catalyst (TWC) model is highly associated with the ability of the model to incorporate the reaction kinetics of the emission process as a lambda function. In this study, we investigated the O2 and H2 concentration profiles of TWC reactions and used them as critical inputs for the development of a global TWC model. We presented the experimental data and global kinetic model showing the impact of thermal degradation on the performance of the TWC. The performance metrics investigated in this study included CH4, NOx, and CO conversions under lean, rich, and dithering light-off conditions to determine the kinetics of oxidation reactions and reduction/reforming/water-gas shift reactions as a function of thermal aging. The O2 and H2 concentrations were measured using mass spectrometry to track the change in the oxidation state of the catalyst and to determine the mechanism of the reactions under these light-off conditions.

This project’s objective was to generate experimental data to evaluate the impact of metals doped B20 on diesel particle filter (DPF) ash loading and performance compared to that of conventional petrodiesel. The effect of metals doped B20 vs. conventional diesel on a DPF was quantified in a laboratory controlled accelerated ash loading study. The ash loading was conducted on two DPFs – one using ULSD fuel and the other on B20 containing metals dopants equivalent to 4 ppm B100 total metals. Engine oil consumption and B20 metals levels were accelerated by a factor of 5, with DPFs loaded to 30 g/L of ash. Details of the ash loading experiment and on-engine DPF performance evaluations are presented in the companion paper (Part I). The DPFs were cleaned, and ash samples were taken from the cleaned material. X-ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD) were conducted on the ash samples.

The project objective was to generate experimental data to evaluate the impact of metals doped B20 on DPF ash loading and performance compared to that of conventional petrodiesel. Accelerated ash loading was conducted on two DPFs – one exposed to regular diesel fuel and the other to B20 containing metal dopants equivalent to 4 ppm B100 total metals (currently total metals are limited to 10 ppm in ASTM D6751, the standard for B100). Periodic performance evaluations were conducted on the DPFs at 10 g/L ash loading intervals. After the evaluations at 30 g/L, the DPF was cleaned with a commercial DPF cleaning machine and another round of DPF evaluations were conducted. A comparison of the effect of ash loading with the two fuels and DPF cleaning is presented. The metals doped B20 fuel resulted in ash that was similar to that deposited when exposed to ULSD (lube oil ash) and exhibited similar ash cleaning removal efficiency.

Stoichiometric natural gas engines with three-way catalysts emit less NOx and CH4 due to their higher efficiency compared to lean-burn natural gas engines. Although hydrothermal aging of three-way catalysts has been extensively studied, a deeper understanding beyond hydrothermal aging is needed to explain real-world performance, especially for natural gas engines with near-zero NOx emissions. In this investigation, field-aged three-way catalysts were characterized to identify the contribution of chemical aging to their overall performance. It was found that the sulfur species on the field-aged TWCs were entirely distributed along the catalyst length, showing a decreasing trend, whereas phosphorous contamination was mainly observed at the inlet section of the three-way catalysts, and the phosphorous concentration declined sharply along the axial length.

Water injection is an effective method for knock control in spark-ignition engines. However, the requirement of a separate water source and the cost and complexity associated with a fully integrated system creates a limitation of this method to be used in volume production engines. The engine exhaust typically contains 10-15% water vapor by volume which could be condensed and potentially stored for future use. In this study, the exhaust condensate composition was assessed for its use as an effective replacement for distilled water. Specifically, condensate samples were collected pre and post-three-way catalyst (TWC) and analyzed for acidity and composition. The composition of the pre and post-TWC condensates was found to be similar however, the pre-TWC condensate was mildly acidic. The mild acidity has the potential to corrode certain components in the intake air circuit.

The confluence of increasing fuel economy requirements and increased use of ethanol as a gasoline blend component has led to various studies into the efficiency and performance benefits of higher octane numbers and high ethanol content fuels in modern engines. As part of a comprehensive study of the autoignition of different fuels in both the CFR octane rating engine and a modern, direct injection, turbocharged spark-ignited engine, a series of fuel blends were prepared with varying composition, octane numbers and ethanol blend levels. The paper reports on the third part of this study where cylinder pressures were recorded for fuels under knocking conditions in both a single-cylinder research engine (SCE), utilizing a GM LHU head and piston, as well as the CFR engines used for octane ratings.

It is widely acknowledged that the CFR octane rating engines are not representative of modern engines and that there is a gap in the quantification of knock severity between the two engine types. As part of a comprehensive study of the autoignition of different fuels in both the CFR octane rating engines and a modern, direct injection, turbocharged spark-ignited engine, a series of fuel blends were tested with varying composition, octane numbers and ethanol blend levels. The paper reports on the fourth part of this study where cylinder pressures were recorded under standard knock conditions in CFR engines under RON and MON conditions using the ASTM prescribed instrumentation. By the appropriate signal conditioning of the D1 detonation pickups on the CFR engines, a quantification of the knock severity was possible that had the same frequency response as a cylinder pressure transducer.

As agencies and governing bodies evaluate the feasibility of reduced emission standards, additional focus has been placed on technology durability. This is seen in proposed updates, which would require Original Equipment Manufacturers (OEMs) to certify engine families utilizing a full useful life (FUL) aftertreatment system. These kinds of proposed rulings would place a heavy burden on the manufacturer to generate FUL components utilizing traditional engine aging methods. Complications in this process will also increase the product development effort and will likely limit the amount of aftertreatment durability testing. There is also uncertainty regarding the aging approach and the representative impact compared to field aged units. Existing methodologies have evolved to account for several deterioration mechanisms that, when controlled, can be utilized to create a flexible aging protocol. As a result, these methodologies provide the necessary foundation for continued development.

The confluence of increasing fuel economy requirements and increased use of ethanol as a gasoline blend component has led to various studies into the efficiency and performance benefits of higher octane numbers and high ethanol content fuels in modern engines. As part of a comprehensive study of the autoignition of different fuels in both the CFR octane rating engine and a modern, direct injection, turbocharged spark ignited engine, a series of fuel blends were prepared with varying composition, octane numbers and ethanol blend levels. The paper reports on the second part of this study where cylinder pressures were recorded for fuels under knocking conditions in both a single cylinder research engine (SCRE), utilizing a GM LHU head and piston, as well as the CFR engines used for octane ratings.

The confluence of fuel economy improvement requirements and increased use of ethanol as a gasoline blend component has led to various studies into the efficiency and performance benefits to be had when using high octane number, high ethanol content fuels in modern engines. As part of a comprehensive study of the autoignition of fuels in both the CFR octane rating engine and a modern, direct injection, turbocharged spark ignited engine, a series of fuel blends were prepared with market relevant ranges of octane numbers and ethanol blends levels. The paper reports on the first part of this study where fuel flow measurements were done on a single cylinder research engine, utilizing a GM LHU combustion system, and then used to predict drive cycle fuel economy. For a range of engine speeds and manifold air pressures, spark timing was adjusted to achieve either the maximum brake torque (MBT) or a matched 50 % mass fraction burnt location.

Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.

Diesel engines are facing increased competition from gasoline engines in the light-duty and small non-road segments, primarily due to the high relative cost of emissions control systems for lean-burn diesel engines. Advancements in gasoline engine technology have decreased the operating cost advantage of diesels and the relatively high initial-cost disadvantage is now too large to sustain a strong business position. SwRI has focused several years of research efforts toward enabling diesel engine combustion systems to operate at stoichiometric conditions, which allows the application of a low-cost three-way catalyst emission control system which has been well developed for gasoline spark-ignited engines. One of the main barriers of this combustion concept is the result of high smoke emissions from poor fuel/air mixing.

Solid and metallic ash particle number (PN) and particulate matter (PM) mass emission measurements were performed on a heavy-duty (HD) on-highway diesel engine and a compressed natural gas (CNG) engine. Measurements were conducted under transient engine operation that included the FTP, WHTC and RMC. Both engines were calibrated to meet CARB ultra low NOX emission target of 0.02 g/hp-hr, a 90% reduction from current emissions limit. The HD diesel engine final exhaust configuration included a number of aftertreatement sub-systems in addition to a selective catalytic reduction filter (SCRF). The stoichiometric CNG engine final configuration included a closed coupled Three Way Catalyst (ccTWC) and an under floor TWC (ufTWC). The aftertreatment systems for both engines were aged for a full useful life (FUL) of 435,000 miles, prior to emissions testing. PM mass emissions from both engines were comparable and well below the US EPA emissions standard.

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.