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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.

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.

In order to further characterize and optimize the performance of Selective Catalytic Reduction (SCR) aftertreatment systems used on heavy-duty diesel engines, an accurately calibrated high-fidelity multi-step global kinetic SCR model and a reduced order estimator for on-board diagnostic (OBD) and control are desirable. In this study, a Cu-zeolite SCR catalyst from a 2010 Cummins ISB engine was experimentally studied in a flow reactor using carefully designed protocols. A 2-site SCR model describing mass transfer and the SCR chemical reaction mechanisms is described in the paper. The model was calibrated to the reactor test data sets collected under temperatures from 200 to 425 °C and SCR space velocities of 60000, 90000, and 120000 hr-1. The model parameters were calibrated using an optimization code to minimize the error between measured and simulated NO, NO₂, N₂O, and NH₃ gas concentration time histories.

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.

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.

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.

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.

The development of new catalytic materials is still dominated by trial and error methods, even though the experimental and theoretical bases for their characterization have improved dramatically in recent years. Although it has been successful, the empirical development of catalytic materials is time consuming and expensive with no guarantee of success. We have been exploring computationally complex but experimentally simple systems to establish a “catalysis by design” protocol that combines the power of theory and experiment. We hope to translate the fundamental insights directly into a complete catalyst system that is technologically relevant. The essential component of this approach is that the catalysts are iteratively examined by both theoretical and experimental methods.

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.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with nitrogen oxides (NOx) emissions standards. In order to better understand fouling mechanisms, eleven field-aged EGR coolers provided by seven different engine manufacturers were characterized using a suite of techniques. Microstructures were characterized using scanning electron microscopy (SEM) and optical microscopy following mounting the samples in epoxy and polishing. Optical microscopy was able to discern the location of hydrocarbons in the polished cross-sections. Chemical compositions were measured using thermal gravimetric analysis (TGA), differential thermal analysis (DTA), gas chromatography-mass spectrometry (GC-MS), x-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS) and x-ray diffraction (XRD). Mass per unit area along the length of the coolers was also measured.

Low temperature combustion engine technologies are being investigated for high efficiency and low emissions. However, such engine technologies often produce higher engine-out hydrocarbon (HC) and carbon monoxide (CO) emissions, and their operating range is limited by the fuel properties. In this study, two different fuels, a US market gasoline containing 10% ethanol (RON 92 E10) and a higher reactivity gasoline (RON 80 E0), were compared on Delphi’s second generation Gasoline Direct-Injection Compression Ignition (Gen 2.0 GDCI) multi-cylinder engine. The engine was evaluated at three operating points ranging from a light load condition (800 rpm/2 bar IMEPg) to medium load conditions (1500 rpm/6 bar and 2000 rpm/10 bar IMEPg). The engine was equipped with two oxidation catalysts, between which was located the exhaust gas recirculation (EGR) inlet. Samples were taken at engine-out, between the catalysts, and at tailpipe locations.

One challenge in meeting emission regulations with catalytic aftertreatment systems is maintaining the proper catalyst temperatures that enable the catalytic devices to perform the emissions reduction. In this study, in-cylinder techniques are used to actively control the temperature of a catalyzed diesel particulate filter (DPF) in order to raise the DPF temperature to induce particulate oxidation. The performance of four strategies is compared for two different starting DPF temperatures (150°C and 300°C) on a 4-cylinder 1.7-liter diesel engine. The four strategies include: (1) addition of extra fuel injection early in the combustion cycle for all four cylinders, (2) addition of extra fuel injection late in the combustion cycle for all four cylinders, (3) operating one-cylinder with extra fuel injection early in the combustion cycle, and (4) operating one-cylinder with extra fuel injection late in the combustion cycle.

Lean NOx trap (LNT) catalysts with different formulations have been characterized on a light-duty diesel engine platform. Two in-cylinder regeneration strategies were used during the study. The reductant chemistry differed for both strategies with one strategy having high levels of CO and H2 and the other strategy having a higher hydrocarbon component. The matrix of LNT catalysts that were characterized included LNTs with various sorbate loads and varying ceria content; the sorbate was Ba. Intra-catalyst measurements of exhaust gas composition were obtained at one quarter, one half, and three quarters of the length of the catalysts to better understand the affect of formulation on performance. Exhaust analysis with FTIR allowed measurement of NH3 and thereby, a measurement of N2 selectivity for the catalysts. Although overall NOx conversion increased with increasing sorbate load, the formation of NH3 increased as well.

In this study, the compression ratio of a commercial 15L heavy-duty diesel engine was lowered and a split injection strategy was developed to promote partially premixed compression ignition (PPCI) combustion. Various low reactivity gasoline-range fuels were compared with ultra-low-sulfur diesel fuel (ULSD) for steady-state engine performance and emissions. Specially, particulate matter (PM) emissions were examined for their mass, size and number concentrations, and further characterized by organic/elemental carbon analysis, chemical speciation and thermogravimetric analysis. As more fuel-efficient PPCI combustion was promoted, a slight reduction in fuel consumption was observed for all gasoline-range fuels, which also had higher heating values than ULSD. Since mixing-controlled combustion dominated the latter part of the combustion process, hydrocarbon (HC) and carbon monoxide (CO) emissions were only slightly increased with the gasoline-range fuels.