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Journal Article

Lean Gasoline Engine Reductant Chemistry During Lean NOx Trap Regeneration

2010-10-25
2010-01-2267
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.
Journal Article

Lean NOx Trap Modeling for Vehicle Systems Simulations

2010-04-12
2010-01-0882
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.
Journal Article

Effects of Rapid High Temperature Cyclic Aging on a Fully-Formulated Lean NOx Trap Catalyst

2009-04-20
2009-01-0634
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.
Technical Paper

Modeling Chemistry in Lean NOx Traps Under Reducing Conditions

2006-10-16
2006-01-3446
A set of elementary surface reactions is proposed for modeling the chemistry in a lean NOx trap during regeneration (reduction of stored NOx). The proposed reaction mechanism can account for the observed product distribution from the trap over a range of temperatures and inlet gas compositions similar to those expected for realistic operation. The mechanism includes many reactions already discussed in the literature, together with some hypothesized reactions that are required to match observations from temperature programmed reactor experiments with a commercial lean NOx trap catalyst. Preliminary results indicate that the NOx trap regeneration and byproduct formation rates can be effectively captured by using a relatively compact set of elementary reactions.
Technical Paper

Rapid In Situ Measurement of Fuel Dilution of Oil in a Diesel Engine using Laser-Induced Fluorescence Spectroscopy

2007-10-29
2007-01-4108
A technique for rapid in situ measurement of the fuel dilution of oil in a diesel engine is presented. Fuel dilution can occur when advanced in-cylinder fuel injection techniques are employed for the purpose of producing rich exhaust for lean NOx trap catalyst regeneration. Laser-induced fluorescence (LIF) spectroscopy is used to monitor the oil in a Mercedes 1.7-liter engine operated on a dynamometer platform. A fluorescent dye suitable for use in diesel fuel and oil systems is added to the engine fuel. The LIF spectra are monitored to detect the growth of the dye signal relative to the background oil fluorescence; fuel mass concentration is quantified based on a known sample set. The technique was implemented with fiber optic probes which can be inserted at various points in the engine oil system. A low cost 532-nm laser diode was used for excitation.
Technical Paper

Rapid Aging of Diesel Lean NOx Traps by High-Temperature Thermal Cycling

2007-04-16
2007-01-0470
In the present study, a bench-flow reactor is used to perform lean/rich thermal cycling on model “Ba+K” LNT catalysts at temperatures of 700, 800, 900 and 1000°C using simulated diesel exhaust gases. Deterioration of NOx performance is measured and the deactivation mechanisms of thermally-aged “Ba+K” LNTs are identified using characterization techniques such as TEM, XRD and EPMA. Results indicate that the deterioration is minimal at 700 and 800°C, however, at aging temperatures exceeding 800°C the severity of thermal aging depends on aging temperature as well as number of aging cycles.
Technical Paper

Characterization of Lean NOx Trap Catalysts with In-Cylinder Regeneration Strategies

2008-04-14
2008-01-0448
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.
Technical Paper

Synergies of PCCI-Type Combustion and Lean NOx Trap Catalysis for Diesel Engines

2008-10-06
2008-01-2493
It is widely recognized that future NOx and particulate matter (PM) emission targets for diesel engines cannot be met solely via advanced combustion over the full engine drive cycle. Therefore some combination of advanced combustion and aftertreatment technologies will be required. In this study, advanced combustion modes operating with a diesel particulate filter (DPF) and a lean NOx trap (LNT) catalyst were evaluated on a 1.7 liter 4-cylinder diesel engine. The combustion approaches included baseline engine operation with and without exhaust gas recirculation (EGR) and one PCCI-type (premixed charge combustion ignition) combustion mode to enable high efficiency clean combustion (HECC). Five steady-state operating conditions were evaluated. At the low load setting the exhaust temperature was too low to enable LNT regeneration and oxidation; however, HECC (low NOx) was achievable.
Technical Paper

Product Selectivity During Regeneration of Lean NOx Trap Catalysts

2006-10-16
2006-01-3441
NOx reduction product speciation during regeneration of a fully formulated lean NOx trap catalyst has been investigated using a bench-scale flow reactor. NH3 and N2O were both observed during the regeneration phase of fast lean/rich cycles that simulated engine operation. Formation of both products increased with higher reductant concentrations and lower temperatures. Steady flow experiments were used to decouple the regeneration reactions from the NOx storage and release processes. This approach enabled a detailed investigation into the reactions that cause both formation and destruction of non-N2 reduction products. Pseudo-steady state experiments with simultaneous flow of NOx and reductant indicated that high concentrations of CO or H2 drive the reduction reactions toward NH3 formation, while mixtures that are stoichiometric for N2 formation favor N2. These experiments also showed that NH3 is readily oxidized by both NO and O2 over the LNT catalyst.
Technical Paper

Intra-Catalyst Reductant Chemistry and Nox Conversion of Diesel Lean Nox Traps at Various Stages of Sulfur Loading

2006-10-16
2006-01-3423
Due to increasingly stringent emissions regulations, Lean NOx Trap (LNT) catalysts are being researched as a potential solution for diesel engine emissions reduction. LNTs are practical for diesel NOx reduction due to their ability to reduce NOx from the O2 rich environment produced by diesel engines. LNTs function by storing NOx on the catalyst surface during efficient lean operation then, under rich conditions, releasing and reducing the trapped NOx. One method of producing this rich environment which regenerates a LNT involves manipulating the fuel injection parameters and throttling the air intake. This process is called in-cylinder regeneration. Experiments will be described here in which a 1.7 L common rail diesel engine has been used to regenerate LNTs at various stages of sulfur exposure, a known poison of the LNT.
Technical Paper

In-Cylinder Production of Hydrogen During Net-Lean Diesel Operation

2006-04-03
2006-01-0212
Hydrogen (H2) is an excellent reductant, and has been shown to be highly effective when introduced into a variety of catalysts such as three-way catalysts, lean NOx traps (LNTs), and hydrocarbon lean NOx catalysts (also termed hydrocarbon selective catalytic reduction (SCR) catalysts). Furthermore, since lean-burn engines offer improved fuel efficiency yet difficult NOx emission control, H2 production during lean operation for the purpose of NOx reduction could be beneficial. On-board generation of hydrogen is being explored via catalytic or plasma-based reformers. A possible alternative to these add-on systems is generation of the H2 in-cylinder with standard fuel injection hardware. This paper details experiments relating to the production and measurement of H2 under net-lean operation in a common-rail diesel engine. In-cylinder fuel control is used to tailor the combustion process such that H2 is generated while maintaining a lean Air:Fuel ratio in the bulk exhaust gas.
Technical Paper

In-Cylinder Regeneration of Lean NOx Trap Catalysts Using Low Temperature Combustion

2006-04-03
2006-01-1416
A Lean NOx Trap (LNT) regeneration method that has shown promise regarding its ability to effectively regenerate the LNT, while not adversely affecting the PM emissions, involves the use of Low Temperature Combustion (LTC). LTC is accomplished by highly diluting the intake charge with EGR.1-3* If enough EGR is applied, the in-cylinder air:fuel mixture, and ensuing exhaust, will become rich, thereby regenerating the LNT. This type of highly dilute combustion tends to be more premixed than diffusion, which can lower engine-out PM and NOx emissions. LTC regeneration has been characterized and results are presented comparing this approach to other approaches for rich, in-cylinder diesel combustion for LNT regeneration.
Technical Paper

Nitrogen Selectivity in Lean NOx Trap Catalysis with Diesel Engine In-Cylinder Regeneration

2005-10-24
2005-01-3876
NOx emissions have traditionally been difficult to control from diesel engines; however, lean NOx trap catalysts have been shown to reduce NOx emissions from diesel engines by greater than 90% under some conditions. It is imperative that lean NOx traps be highly selective to N2 to achieve the designed NOx emissions reduction. If selectivity for NOx reduction to NH3 or N2O is significant then, ultimately, higher levels of pollution or greenhouse emissions will result. Here studies of the N2 selectivity of lean NOx trap regeneration with in-cylinder techniques are presented. Engine dynamometer studies with a light-duty engine were performed, and a lean NOx trap in the exhaust system was regenerated by controlling in-cylinder fuel injection timing and amounts to achieve rich exhaust conditions. NH3 and N2O emissions were analyzed with FTIR spectroscopy.
Technical Paper

Assessing Reductant Chemistry During In-Cylinder Regeneration of Diesel Lean NOx Traps

2004-10-25
2004-01-3023
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.
Technical Paper

Time-Resolved Laser-Induced Incandescence Measurements of Particulate Emissions During Enrichment for Diesel Lean NOx Trap Regeneration

2005-04-11
2005-01-0186
Laser-induced incandescence is used to measure time-resolved diesel particulate emissions for two lean NOx trap regeneration strategies that utilize intake throttling and in-cylinder fuel enrichment. The results show that when the main injection event is increased in duration and delayed 13 crank-angle degrees, particulate emissions are very high. For a repetitive pattern of 3 seconds of rich regeneration followed by 27 seconds of NOx-trap loading, we find a monotonic increase in particulate emissions during the loading intervals that approaches twice the initial baseline particulate level after 1000 seconds. In contrast, particulate emissions during the regeneration intervals are constant throughout the test sequence.
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