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Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. Using an accelerated aging procedure, a set of production exhaust systems from a 2011 Ford F250 equipped with a 6.7L diesel engine have been aged to an equivalent of 150,000 miles of thermal aging and metal exposure. These exhaust systems included a diesel oxidation catalyst (DOC), selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ULSD containing no measureable metals, B20 containing sodium, B20 containing potassium and B20 containing calcium. Metals levels were selected to simulate the maximum allowable levels in B100 according to the ASTM D6751 standard. Analysis of the aged catalysts included Federal Test Procedure emissions testing with the systems installed on a Ford F250 pickup, bench flow reactor testing of catalyst cores, and electron probe microanalysis (EPMA).

Diesel particulate filters (DPF) are a common component in emission-control systems of modern clean diesel vehicles. Several DPF materials have been used in various applications. Silicone Carbide (SiC) is common for passenger vehicles because of its thermal robustness derived from its high specific gravity and heat conductivity. However, a segmented structure is required to relieve thermal stress due to SiC's higher coefficient of thermal expansion (CTE). Cordierite (Cd) is a popular material for heavy-duty vehicles. Cordierite which has less mass per given volume, exhibits superior light-off performance, and is also adequate for use in larger monolith structures, due to its lower CTE. SiC and cordierite are recognized as the most prevalent DPF materials since the 2000's. The DPF traps not only combustible particles (soot) but also incombustible ash. Ash accumulates in the DPF and remains in the filter until being physically removed.

The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which las smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

Rare earths are a group of elements whose availability has been of concern due to monopolistic supply conditions and environmentally unsustainable mining practices. To evaluate the risks of rare earths availability to automakers, a first step is to determine raw material content and value in vehicles. This task is challenging because rare earth elements are used in small quantities, in a large number of components, and by suppliers far upstream in the supply chain. For this work, data on rare earth content reported by vehicle parts suppliers was assessed to estimate the rare earth usage of a typical conventional gasoline engine midsize sedan and a full hybrid sedan. Parts were selected from a large set of reported parts to build a hypothetical typical mid-size sedan. Estimates of rare earth content for vehicles with alternative powertrain and battery technologies were made based on the available parts' data.

The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which has smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

Three established mechanical test specimen geometries and test methods used to evaluate mechanical properties of brittle materials are adapted to the diesel particulate filter (DPF) architecture to evaluate failure initiation stress and apparent elastic modulus of the ceramics comprising DPFs. The three custom-designed test coupons are harvested out of DPFs to promote a particular combination of orientation of crack initiation and crack plane. The testing of the DPF biaxial flexure disk produces a radial tensile stress and a crack plane parallel with the DPF's longitudinal axis. The testing of the DPF sectored flexural specimen produces axial tension at the DPF's OD and a crack plane perpendicular to the DPF's longitudinal axis. The testing of the DPF o-ring specimen produces hoop tension at the DPF's original outer diameter (OD) and at the inner diameter of the test coupon, and a crack plane parallel to the DPF's longitudinal axis.

The accumulation of soot and lubrication-derived ash particles in a diesel particulate filter (DPF) increases exhaust flow restriction and negatively impacts engine efficiency. Previous studies have described the macroscopic phenomenon and general effects of soot and ash accumulation on filter pressure drop. In order to enhance the fundamental understanding, this study utilized a novel apparatus that of a dual beam scanning electron microscope (SEM) and focused ion beam (FIB), to investigate microscopic details of soot and ash accumulation in the DPF. Specifically, FIB provides a minimally invasive technique to analyze the interactions between the soot, ash, catalyst/washcoat, and DPF substrate with a high degree of measurement resolution. The FIB utilizes a gallium liquid metal ion source which produces Ga+ ions of sufficient momentum to directionally mill away material from the soot, ash, and substrate layers on a nm-μm scale.

Current CJ-4 lubricant specifications place chemical limits on diesel engine oil formulations to minimize the accumulation of lubricant-derived ash in diesel particulate filters (DPF). While lubricant additive chemistry plays a strong role in determining the amount and type of ash accumulated in the DPF, a number of additional factors play important roles as well. Relative to soot particles, whose residence time in the DPF is short-lived, ash particles remain in the filter for a significant fraction of the filter's useful life. While it is well-known that the properties (packing density, porosity, permeability) of soot deposits are primarily controlled by the local exhaust conditions at the time of particle deposition in the DPF, the cumulative operating history of the filter plays a much stronger role in controlling the properties and distribution of the accumulated ash.

We utilize physically-based models for diesel exhaust catalytic oxidation and urea-based selective catalytic NOx reduction to study their impact on drive cycle performance of hypothetical light-duty diesel-powered hybrid and plug-in hybrid vehicles (HEVs and PHEVs). The models have been implemented as highly flexible SIMULINK block modules that can be used to study multiple engine-aftertreatment system configurations. The parameters of the NOx reduction model have been adjusted to reflect the characteristics of commercially available Cu-zeolite catalysts, which are of widespread current interest. We demonstrate application of these models using the Powertrain System Analysis Toolkit (PSAT) software for vehicle simulations, along with a previously published methodology that accounts for emissions and temperature transients in the engine exhaust.

The leading approach for reduction of NOx from diesel engines is selective catalytic reduction employing urea as a reductant (NH₃- or urea-SCR). For passenger vehicles, the best known NH₃-SCR catalysts are Cu-ZSM-5 and Fe-ZSM-5 and have been shown to function very well in a narrow temperature range. This technology is not directly transferable to off-road diesel engines which operate under a different duty cycle resulting in exhaust with different fractions of components than are present in passenger vehicle emissions. Our results show that Cu-ZSM-5 exhibits 90% NOx reduction efficiency in 250-450°C range while Fe-ZSM-5 is highly effective in 350-550°C range for off-road engines. However, a combination of these catalysts cannot efficiently reduce NOx in 150-650°C which is the desirable range for deployment in off-road diesel engines. In our efforts to increase the effective range of these catalysts, we initiated efforts to modify these catalysts by catalyst promoters.

An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

Lean NOx Trap (LNT) catalysts can effectively reduce NOx from lean engine exhaust. Significant research for LNTs in diesel engine applications has been performed and has led to commercialization of the technology. For lean gasoline engine applications, advanced direct injection engines have led to a renewed interest in the potential for lean gasoline vehicles and, thereby, a renewed demand for lean NOx control. To understand the gasoline-based reductant chemistry during regeneration, a BMW lean gasoline vehicle has been studied on a chassis dynamometer. Exhaust samples were collected and analyzed for key reductant species such as H₂, CO, NH₃, and hydrocarbons during transient drive cycles. The relation of the reductant species to LNT performance will be discussed. Furthermore, the challenges of NOx storage in the lean gasoline application are reviewed.

Accurate knowledge of diesel particulate filter (DPF) particulate matter (PM) loading is critical for robust and efficient operation of the combined engine-exhaust aftertreatment system. Furthermore, upcoming on-board diagnostics regulations require on-board technologies to evaluate the status of the DPF. This work describes the application of radio frequency (RF) - based sensing techniques to accurately measure DPF particulate matter levels. A 1.9L GM turbo diesel engine and a DPF with an RF-sensor were studied. Direct comparisons between the RF measurement and conventional pressure-based methods were made. Further analysis of the particulate matter loading rates was obtained with a mass-based total PM emission measurement instrument (TEOM) and DPF gravimetric measurements.

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.

A transient, one-dimensional lean NOx trap (LNT) model is described and implemented for vehicle systems simulations. The model accounts for conservation of chemical species and thermal energy, and includes the effects of O₂ storage and NOx storage (in the form of nitrites and nitrates). Nitrites and nitrates are formed by diffusion of NO and NO₂, respectively, into sorbent particles, and reaction rates are controlled by chemical kinetics and solid-phase diffusion. The model also accounts for thermal aging and sulfation by means of empirical correlations, which have been derived from laboratory experiments. Example simulation results using the Powertrain Systems Analysis Toolkit (PSAT) are presented.

Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.

Ash accumulation in diesel particulate filters, mostly from essential lubricant additives, decreases the filter's soot storage capacity, adversely affects fuel economy, and negatively impacts the filter's service life. While the adverse effects of ash accumulation on DPF performance are well known, the underlying mechanisms controlling these effects are not. To address these issues, results of detailed measurements with specially formulated lubricants, correlating ash properties to individual lubricant additives and their effects on DPF pressure drop, are presented. Investigations using the specially-formulated lubricants showed ash consisting primarily of calcium sulfates to exhibit significantly increased flow resistance as opposed to ash primarily composed of zinc phosphates. Furthermore, ash accumulated along the filer walls was found to be packed approximately 25% denser than ash accumulated in the channel end-plugs.

A hybrid LNT+SCR system is used to control NOx from a light-duty diesel engine with in-cylinder regeneration controls. A diesel oxidation catalyst and diesel particulate filter are upstream of the LNT and SCR catalysts. Ultraviolet (UV) adsorption spectroscopy performed directly in the exhaust path downstream of the LNT and SCR catalysts is used to characterize NH3 production and utilization in the system. Extractive exhaust samples are analyzed with FTIR and magnetic sector mass spectrometry (H2) as well. Furthermore, standard gas analyzers are used to complete the characterization of exhaust chemistry. NH3 formation increases strongly with extended regeneration (or “over regeneration”) of the LNT, but the portion of NOx reduction occurring over the SCR catalyst is limited by the amount of NH3 produced as well as the amount of NOx available downstream of the LNT. Control of lean-rich cycling parameters enables control of the ratio of NOx reduction between the LNT and SCR catalysts.

Advanced diesel combustion regimes such as High Efficiency Clean Combustion (HECC) offer the benefits of reduced engine out NOx and particulate matter (PM) emissions. Lower PM emissions during advanced combustion reduce the demand on diesel particulate filters (DPFs) and can, thereby, reduce the fuel penalty associated with DPF regeneration. In this study, a SiC DPF was loaded and regenerated on a 1.7-liter 4-cylinder diesel engine operated in conventional and advanced combustion modes at different speed and load conditions. A diesel oxidation catalyst (DOC) and a lean NOx trap (LNT) were also installed in the exhaust stream. Five steady-state speed and load conditions were weighted to estimate Federal Test Procedure (FTP) fuel efficiency. The DPF was loaded using lean-rich cycling with frequencies that resulted in similar levels of NOx emissions downstream of the LNT.

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.