Josh A. Pihl

Product Selectivity During Regeneration of Lean NOx Trap Catalysts

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. These observations were incorporated into a schematic of the regeneration process that takes into account the spatial and temporal variations occurring within the catalyst.

Effective Model for Prediction of N2O and NH3 Formation During the Regeneration of NOx Storage Catalyst

In this paper we propose an effective global kinetic model that allows prediction of N2O and NH3 formation during the reduction of stored NOx in dependence on the composition of the rich mixture (H2/CO/C3H6), actual operating temperature, and length of regeneration period. A bench flow reactor equipped with a high-speed FTIR was used to measure dynamic evolution of gas components during periodic lean/rich operation of a fully formulated NSRC catalyst (PtPdRh/Ba/Ce–Zr/Mg–Al/Al2O3).

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

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 N 2 to achieve the designed NOx emissions reduction. If selectivity for NOx reduction to NH 3 or N 2 O is significant then, ultimately, higher levels of pollution or greenhouse emissions will result. Here studies of the N 2 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. NH 3 and N 2 O emissions were analyzed with FTIR spectroscopy. Both engine and bench experiments show that excess reductant delivery during regeneration leads to high NH 3 emissions and poor N 2 selectivity. Specific design of in-cylinder regeneration techniques that minimize excess reductant or allow O 2 purge can optimize N 2 selectivity of the lean NOx trap catalyst.

A SCR Model Calibration Approach with Spatially Resolved Measurements and NH3 Storage Distributions

The selective catalytic reduction (SCR) is a technology used for reducing NOx emissions in the heavy-duty diesel (HDD) engine exhaust. In this study, the spatially resolved capillary inlet infrared spectroscopy (Spaci-IR) technique was used to study the gas concentration and NH3 storage distributions in a SCR catalyst, and to provide data for developing a SCR model to analyze the axial gaseous concentration and axial distributions of NH3 storage. A two-site SCR model is described for simulating the reaction mechanisms. The model equations and a calculation method was developed using the Spaci-IR measurements to determine the NH3 storage capacity and the relationships between certain kinetic parameters of the model. A calibration approach was then applied for tuning the kinetic parameters using the spatial gaseous measurements and calculated NH3 storage as a function of axial position instead of inlet and outlet gaseous concentrations of NO, NO2, and NH3. The equations and the approach for determining the NH3 storage capacity of the catalyst and a method of dividing the NH3 storage capacity between the two storage sites are presented. It was determined that the kinetic parameters of the adsorption and desorption reactions have to follow certain relationships for the model to simulate the experimental data. The modeling results served as a basis for developing full model calibrations to SCR lab reactor and engine data and state estimator development as described in the references (Song et al. 2013a, b; Surenahalli et al. 2013).

Lean NOx Trap Chemistry Under Lean-Gasoline Exhaust Conditions: Impact of High NOx Concentrations and High Temperature

The primary technical barrier to deployment of fuel saving lean gasoline engines is NOx emissions control. We conducted automated flow reactor experiments on a commercial LNT catalyst to identify opportunities and challenges associated with the higher temperatures and higher NOx concentrations expected in lean gasoline applications. Overall NOx conversion was quite high at low to moderate temperatures, but dropped off at high temperatures. The decrease in NOx conversion with temperature was worse for higher inlet NOx concentrations. As expected from equilibrium considerations, the catalyst stored more NOx under higher gas phase NOx concentrations, but that NOx was rapidly released during the rich phase and slipped out of the catalyst before it could be converted to N2 by incoming reductant. This rich phase NOx release was the primary factor limiting performance of the catalyst at high temperatures, and resulted in significant spikes of NOx that would likely exceed any not-to-exceed regulated emissions levels. N2O production was also significant, and increased with NOx concentration. The catalyst made very little NH3 at high temperatures. NH3 yield was significant at the lowest operating temperature studied, but it decreased with increasing NOx concentration.

Fe-Zeolite Functionality, Durability, and Deactivation Mechanisms in the Selective Catalytic Reduction (SCR) of NOx with Ammonia

Since the introduction of the first emissions control regulations in the 1970s and 1980s [1], catalysis has been implemented extensively to maintain compliance and dramatically reduce the harmful pollutants emitted from combustion engines. For stoichiometric exhaust, primarily from gasoline-powered vehicles, precious metals, or platinum-group metals (PGM), such as Pt, Pd, and Rh, have been the hallmark of three-way catalysis, e.g., [2, 3, 4], as they are highly active in oxidation of carbon monoxide (CO) and hydrocarbons (HCs) as well as the reduction of nitrogen oxides (NOx). The chemistry behind these reactions is equilibrium driven, as the more benign products of CO2, H2O, and N2 are thermodynamically favored. However, these catalysts only function properly if the exhaust is at or near stoichiometric conditions. As a result, gasoline vehicle manufacturers began designing their engine control systems to operate with stoichiometric air/fuel ratios to optimize catalyst performance and minimize emissions. The need for more fuel-efficient vehicles, both with respect to increasing fuel costs and future CO2 emissions regulations, is driving vehicle manufacturers to investigate more efficient combustion strategies, such as lean-burn gasoline, or increase production of more fuel-efficient diesel vehicles.

In-Cylinder Reaction Chemistry and Kinetics During Negative Valve Overlap Fuel Injection Under Low-Oxygen Conditions

Fuel injection into the negative valve overlap (NVO) period is a common method for controlling combustion phasing in homogeneous charge compression ignition (HCCI) as well as other forms of advanced combustion. During this event, at least a portion of the fuel hydrocarbons can be converted to products containing significant levels of H2 and CO, as well as other short chain hydrocarbons by means of thermal cracking, watergas shift, and partial oxidation reactions, depending on the availability of oxygen and the time-temperature-pressure history. The resulting products alter the autoignition properties of the combined fuel mixture for HCCI. Fuel-rich chemistry in a partial oxidation environment is also relevant to other high efficiency engine concepts (e.g., the dedicated EGR (D-EGR) concept from SWRI). In this study, we used a unique 6-stroke engine cycle to experimentally investigate the chemistry of a range of fuels injected during NVO under low oxygen conditions. Fuels investigated included iso-octane, iso-butanol, ethanol, and methanol. Products from NVO chemistry were highly dependent on fuel type and injection timing, with iso-octane producing less than 1.5% hydrogen and methanol producing more than 8%. We compare the experimental trends with CHEMKIN (single zone, 0-D model) predictions using multiple kinetic mechanisms available in the current literature. Our primary conclusion is that the kinetic mechanisms investigated are unable to accurately predict the magnitude and trends of major species we observed.Copyright

Effect of Hydrocarbon Emissions From PCCI-Type Combustion on the Performance of Selective Catalytic Reduction Catalysts

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. Subsequently, the NOx reduction performance of the exposed catalysts was evaluated on a laboratory bench-reactor fed with simulated exhaust. The Fe-zeolite NOx conversion efficiency was significantly degraded, especially at low temperatures (<250 C), after the catalyst was exposed to the engine exhaust. The degradation of the Fe-zeolite performance was similar for both combustion modes. The Cu-zeolite was much more resistant to HC fouling than the Fe-zeolite catalyst. In the case of the Cu-zeolite, PCCI exhaust had a more significant impact than the exhaust from conventional combustion on the NOx conversion efficiency. For all cases, the clean catalyst performance was recovered after heating to 600 C. GC-MS analysis of the HCs adsorbed to the catalyst surface provided insights into the observed NOx reduction performance trends.

Simulation of lean NOx trap performance with microkinetic chemistry and without mass transfer.

A microkinetic chemical reaction mechanism capable of describing both the storage and regeneration processes in a fully formulated lean NO{sub x} trap (LNT) is presented. The mechanism includes steps occurring on the precious metal, barium oxide (NO{sub x} storage), and cerium oxide (oxygen storage) sites of the catalyst. The complete reaction set is used in conjunction with a transient plug flow reactor code to simulate not only conventional storage/regeneration cycles with a CO/H{sub 2} reductant, but also steady flow temperature sweep experiments that were previously analyzed with just a precious metal mechanism and a steady state code. The results show that NO{sub x} storage is not negligible during some of the temperature ramps, necessitating a re-evaluation of the precious metal kinetic parameters. The parameters for the entire mechanism are inferred by finding the best overall fit to the complete set of experiments. Rigorous thermodynamic consistency is enforced for parallel reaction pathways and with respect to known data for all of the gas phase species involved. It is found that, with a few minor exceptions, all of the basic experimental observations can be reproduced with these purely kinetic simulations, i.e., without including mass-transfer limitations. In addition to accounting for normal cycling behavior, the final mechanism should provide a starting point for the description of further LNT phenomena such as desulfation and the role of alternative reductants.

Experimental Studies for CPF and SCR Model, Control System, and OBD Development for Engines Using Diesel and Biodiesel Fuels

The research carried out on this project developed experimentally validated Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), and Selective Catalytic Reduction (SCR) high‐fidelity models that served as the basis for the reduced order models used for internal state estimation. The high‐fidelity and reduced order/estimator codes were evaluated by the industrial partners with feedback to MTU that improved the codes. Ammonia, particulate matter (PM) mass retained, PM concentration, and NOX sensors were evaluated and used in conjunction with the estimator codes. The data collected from PM experiments were used to develop the PM kinetics using the high‐fidelity DPF code for both NO2 assisted oxidation and thermal oxidation for Ultra Low Sulfur Fuel (ULSF), and B10 and B20 biodiesel fuels. Nine SAE papers were presented and this technology transfer process should provide the basis for industry to improve the OBD and control of urea injection and fuel injection for active regeneration of the PM in the DPF using the computational techniques developed. This knowledge will provide industry the ability to reduce the emissions and fuel consumption from vehicles in the field. Four MS and three PhD Mechanical Engineering students were supported on this project and their thesis research provided them with expertise in experimental, modeling, and controls in aftertreatment systems.