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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.

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.

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.

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.

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.

One field-returned DPF loaded with a high amount of ash is examined using experimental and modeling approaches. The ash-related design factors are collected by coupling the inspection results from terahertz spectroscopy with a calibrated DPF model. The obtained ash packing density, ash layer permeability and ash distribution profile are then used in the simulation to assess the ash impact on DPF backpressure and regeneration behaviors. The following features have been observed during the simulation: 1 The ash packing density, ash layer permeability and ash distribution profile should be collected at the same time to ensure the accurate prediction of ash impact on DPF backpressure. Missing one ash property could mislead the measurement of the other two parameters and thus affects the DPF backpressure estimation. 2 The ash buildup would gradually increase the frequency for the backpressure-based active soot regeneration.

This work examines the effect of valve timing during cold crank-start and cold fast-idle (1200 rpm, 2 bar NIMEP) on the emissions of hydrocarbons (HC) and particulate mass and number (PM/PN). Four different cam-phaser configurations are studied in detail: 1. Baseline stock valve timing. 2. Late intake opening/closing. 3. Early exhaust opening/closing. 4. Late intake phasing combined with early exhaust phasing. Delaying the intake valve opening improves the mixture formation process and results in more than 25% reduction of the HC and of the PM/PN emissions during cold crank-start. Early exhaust valve phasing results in a deterioration of the HC and PM/PN emissions performance during cold crank-start. Nevertheless, early exhaust valve phasing slightly improves the HC emissions and substantially reduces the particulate emissions at cold fast-idle.

The increasing use of gasoline direct injection (GDI) engines coupled with the implementation of new particulate matter (PM) and particle number (PN) emissions regulations requires new emissions control strategies. Gasoline particulate filters (GPFs) present one approach to reduce particle emissions. Although primarily composed of combustible material which may be removed through oxidation, particle also contains incombustible components or ash. Over the service life of the filter the accumulation of ash causes an increase in exhaust backpressure, and limits the useful life of the GPF. This study utilized an accelerated aging system to generate elevated ash levels by injecting lubricant oil with the gasoline fuel into a burner system. GPFs were aged to a series of levels representing filter life up to 150,000 miles (240,000 km). The impact of ash on the filter pressure drop and on its sensitivity to soot accumulation was investigated at specific ash levels.

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.

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.

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.

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.

Titanium dioxide supported vanadium oxide catalysts have been successfully utilized for the selective catalytic reduction (SCR) of nitrogen oxides emitted from both stationary and mobile sources. Because of their cost and performance advantages in certain applications, vanadium-based SCR catalysts are now also being considered for integration into some U.S. Tier IV off-highway aftertreatment systems. However, concern exists that toxic vanadium compounds, such as vanadium pentoxide, could be released from these catalysts as a result of mechanical attrition or high temperature volatility. An experimental study has been conducted to compare various techniques for measuring the release of particle and vapor-phase vanadium from SCR catalysts. Previous research has utilized a powder reactor-based method to measure the vapor-phase release of vanadium, but there are inherent limitations to this technique.

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.

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.