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Urea-selective catalytic reduction (SCR) catalysts are the leading aftertreatment technology for diesel engines, but there are major challenges associated with meeting future NOx emission standards, especially under transient drive cycle conditions that include large swings in exhaust temperatures. Here we present a simplified, transient, one-dimensional integral model of NOx reduction by NH₃ on a commercial small-pore Cu-zeolite urea-SCR catalyst for which detailed kinetic parameters have not been published. The model was developed and validated using data acquired from bench reactor experiments on a monolith core, following a transient SCR reactor protocol. The protocol incorporates NH₃ storage, NH₃ oxidation, NO oxidation and three global SCR reactions under isothermal conditions, at three space velocities and at three NH₃/NOx ratios.

The Magnesium Front End Research and Development (MFERD) project under the sponsorship of Canada, China, and USA aims to develop key technologies and a knowledge base for increased use of magnesium in automobiles. The primary goal of this life cycle assessment (LCA) study is to compare the energy and potential environmental impacts of advanced magnesium based front end parts of a North American-built 2007 GM-Cadillac CTS using the current steel structure as a baseline. An aluminium front end is also considered as an alternate light structure scenario. A “cradle-to-grave” LCA is conducted by including primary material production, semi-fabrication production, autoparts manufacturing and assembly, transportation, use phase, and end-of-life processing of autoparts. This LCA study was done in compliance with international standards ISO 14040:2006 [1] and ISO 14044:2006 [2].

One scenario for reducing engine out NOx in a spark ignition engine is to introduce small amounts of supplemental hydrogen to the combustion process. The supplemental hydrogen enables a gasoline engine to run lean where NOx emissions are significantly reduced and engine efficiency is increased relative to stoichiometric operation. This paper reports on a mass and energy balance model that has been developed to evaluate the overall system efficiencies of a thermal reformer-heat exchanger system capable of delivering hydrogen to the air intake of a gasoline engine. The mass and energy balance model is utilized to evaluate the conditions where energy losses associated with fuel reformation may be offset by increases in engine efficiencies.

Internal combustion engines are operated under conditions of high exhaust gas recirculation (EGR) to reduce NOx emissions and promote enhanced combustion modes such as HCCI. However, high EGR under certain conditions also promotes nonlinear feedback between cycles, leading to the development of combustion instabilities and cyclic variability. We employ a two-zone phenomenological combustion model to simulate the onset of combustion instabilities under highly dilute conditions and to illustrate the impact of these instabilities on emissions and fuel efficiency. The two-zone in-cylinder combustion model is coupled to a WAVE engine-simulation code through a Simulink interface, allowing rapid simulation of several hundred successive engine cycles with many external engine parametric effects included.

This project team conducted a life-cycle-based environmental evaluation of new, lightweight materials (e.g., titanium, magnesium) used in two concept 3XVs -- i.e., automobiles that are three times more fuel efficient than today's automobiles -- that are being designed and developed in support of the Partnership for a New Generation of Vehicles (PNGV) program. The two concept vehicles studied were the DaimlerChrysler ESX2 and the Ford P2000. Data for this research were drawn from a wide range of sources, including: the two automobile manufacturers; automobile industry reports; government and proprietary databases; past life-cycle assessments; interviews with industry experts; and models.

Plug-in hybrid electric vehicle (PHEV) technologies have the potential for considerable petroleum consumption reductions, possibly at the expense of increased tailpipe emissions due to multiple “cold” start events and improper use of the engine for PHEV specific operation. PHEVs operate predominantly as electric vehicles (EVs) with intermittent assist from the engine during high power demands. As a consequence, the engine can be subjected to multiple cold start events. These cold start events may have a significant impact on the tailpipe emissions due to degraded catalyst performance and starting the engine under less than ideal conditions. On current hybrid electric vehicles (HEVs), the first cold start of the engine dictates whether or not the vehicle will pass federal emissions tests. PHEV operation compounds this problem due to infrequent, multiple engine cold starts.

Thermal conductivity detection has long been used in gas chromatography to detect hydrogen and other diatomic gases in a gas sample. Thermal conductivity instruments that are not coupled to gas chromatographs are useful for detecting hydrogen in binary gas mixtures, but suffer from significant cross-interference from other gas species that are separated when the detector is used with a gas chromatograph. This study reports a method for using a commercially-available thermal conductivity instrument to detect and quantify hydrogen in a diesel exhaust stream. The instrument time response of approximately 40 seconds is sufficient for steady-state applications. Cross-interference from relevant gas species are quantified and discussed. Measurement uncertainty associated with the corrections for the various species is estimated and practical implications for use of the instrument and method are discussed.

An alternative approach is presented for the regression of response data on predictor variables that are not logically or physically separable. The methodology is demonstrated by its application to a data set of heavy-duty diesel emissions. Because of the covariance of fuel properties, it is found advantageous to redefine the predictor variables as vectors, in which the original fuel properties are components, rather than as scalars each involving only a single fuel property. The fuel property vectors are defined in such a way that they are mathematically independent and statistically uncorrelated. The available data set is not considered adequate for the development of a full-fledged emission model. Nevertheless, the data clearly show that only a few basic patterns of fuel-property variation affect emissions and that the number of these patterns is considerably less than the number of variables initially thought to be involved.

This work explores pathways to achieve diesel-like, high-efficiency combustion with stoichiometric 3-way catalyst compatible spark ignition (SI). A high stroke-to-bore engine design (1.5:1) with cooled exhaust gas recirculation (EGR) and high compression ratio (rc) was used to improve engine efficiency by up to 30% compared with a production turbocharged gasoline direct injection spark ignition engine. To achieve efficiency improvements, engine experiments were coupled with computational fluid dynamics simulations to guide and explain experimental trends between the original engine and the high stroke-to-bore ratio design (1.5:1). The effects of EGR and late intake valve closing (IVC) and fuel characteristics are investigated through their effects on knock mitigation. Direct injection of 91 RON E10 gasoline, 99 RON E0 gasoline, and liquified petroleum gas (i.e., propane/autogas) were evaluated with geometric rc ranging from 13.3:1 to 16.8:1.

Lean gasoline engines offer greater fuel economy than the common stoichiometric gasoline engine, but the current three way catalyst (TWC) on stoichiometric engines is unable to control nitrogen oxide (NOX) emissions in oxidizing exhaust. For these lean gasoline engines, lean NOX emission control is required to meet existing Tier 2 and upcoming Tier 3 emission regulations set by the U.S. Environmental Protection Agency (EPA). While urea-based selective catalytic reduction (SCR) has proven effective in controlling NOX from diesel engines, the urea storage and delivery components can add significant size and cost. As such, onboard NH3 production via a passive SCR approach is of interest. In a passive SCR system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean operation, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst.

A commercial three-way catalyst (TWC) was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential low cost approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. NH3 generation was evaluated at different air-fuel equivalence ratios at multiple engine speed and load conditions. Near complete conversion of NOX to NH3 was achieved at λ=0.96 for nearly all conditions studied. At the λ=0.96 condition, HC emissions were relatively minimal, but CO emissions were significant.

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.

A modified Mercedes 1.7-liter, direct-injection diesel engine was operated in both normal and high-efficiency clean combustion (HECC) combustion modes. Four steady-state engine operating points that were previously identified by the Ad-hoc fuels working group were used as test points to allow estimation of the hot-start FTP-75 emissions levels in both normal and HECC combustion modes. The results indicate that operation in HECC modes generally produce reductions in NOX and PM emissions at the expense of CO, NMHC, and H2CO emissions. The FTP emissions estimates indicate that aftertreatment requirements for NOX are reduced, while those for PM may not be impacted. Cycle-average aftertreatment requirements for CO, NMHC, and H2CO may be challenging, especially at the lowest temperature conditions.

An optical-based sensor for detecting particulate matter (PM) in diesel engine exhaust has been demonstrated. The position of the sensor during the experiments was the exhaust manifold prior to the turbocharger. The sensor is constructed of fiber optics which transmit 532-nm laser light into the exhaust pipe and collect backscattered light in a 180° geometry. Due to the optical nature of the probe, PM sensing can occur at high temporal rates. Experiments conducted by changing the fuel injection properties of one cylinder of a four cylinder engine demonstrated that the sensor can resolve cycle dependent events. The feasibility of the probe for examining PM emissions in the exhaust manifold will be discussed.

Operation of spark-ignition (SI) engines with high levels of charge dilution through exhaust gas recirculation (EGR) achieves significant engine efficiency gains while maintaining stoichiometric operation for compatibility with three-way catalysts. Dilution levels, however, are limited by cyclic variability - including significant numbers of misfires - that becomes more pronounced with increasing dilution. This variability has been shown to have both stochastic and deterministic components. Stochastic effects include turbulence, mixing variations, and the like, while the deterministic effect is primarily due to the nonlinear dependence of flame propagation rates and ignition characteristics on the charge composition, which is influenced by the composition of residual gases from prior cycles.

As interest has grown in diesel emissions and diesel engine aftertreatment, so has the importance of analyzing all components of the exhaust. One of the more costly and difficult measurements to make is the collection and analysis of semivolatile organic compounds (SOCs) in the exhaust. These compounds include alkane and alkenes from C12-C24, and the 2-5 ring polycyclic aromatic hydrocarbons (PAH). These compounds can be present in both the particulate (i.e. on the filter) and gaseous phase, and cannot be collected with bag samples. Typically, a sorbent is used downstream of the particulate collection filters to collect these compounds. Sorbent phases include polyurethane foam (PUF), Tenax™, XAD-type resins, and activated carbon. The SOCs are removed from the sorbent either by solvent extraction (PUF and XAD) or thermal desorption (Tenax™ and activated carbon). Each of these methods have advantages and disadvantages.

Lean NOx Trap (LNT) catalysts are capable of reducing NOx in lean exhaust from diesel engines. NOx is stored on the catalyst during lean operation; then, under rich exhaust conditions, the NOx is released from and reduced by the catalyst. The process of NOx release and reduction is called regeneration. One method of obtaining the rich conditions for regeneration is to inject additional fuel into the engine cylinders while throttling the engine intake air flow to effectively run the engine at rich air:fuel ratios; this method is called “in-cylinder” regeneration. In-cylinder regeneration of LNT catalysts has been demonstrated and is a candidate emission control technique for commercialization of light-duty diesel vehicles to meet future emission regulations. In the study presented here, a 1.7-liter diesel engine with a LNT catalyst system was used to evaluate in-cylinder regeneration techniques.

A high-resolution corrosion probe was placed within the airhorn section of the exhaust gas recirculation (EGR) loop of a heavy-duty diesel engine. The corrosion rate of the mild-steel probe elements was evaluated as a function of fuel sulfur level, EGR fraction, dewpoint margin, and humidity. No significant corrosion was observed while running the engine using a No. 2 grade, < 15ppm sulfur diesel fuel; however, high corrosion rates were observed with No. 2 diesel fuel (∼350 ppm sulfur) while condensing water in the EGR loop. The rate of corrosion on the mild steel elements increased with increasing levels of sulfate in the condensate. However, the engine conditions influencing the sulfate level were not clearly identified in this study.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

Computational approaches have been limited to examining catalytic processes using models that have been greatly simplified in comparison to real catalysts. Experimental studies, especially on emission treatment catalysts, have primarily focused on fully formulated systems. Thus, there remains a knowledge gap between theory and experiments. We combine the power of theory and experiment for atomistic design of catalytically active sites that can translate the fundamental insights gained directly to a catalyst system suitable for technical deployment. In this article, we describe our results on a model platinum-alumina catalyst that is a common constituent of emission treatment catalysts such as three-way, NOx trap, oxidation, and HC-SCR catalysts. We present theoretical and experimental studies of the oxidation and reactivity of Pt catalyst clusters towards O, CO, and NOx.