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The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst 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. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which las smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

The paper will discuss the design and development of heavy-duty diesel engines to meet the US EPA 2010 on-highway standards - 0.2 g/HP-hr NOx and 0.01 g/HP-hr particulate matter (PM). In meeting these standards a combination of in-cylinder control and aftertreatment control for both NOx and particulate has been used. For NOx control, a combination of cooled exhaust gas recirculation (EGR) and selective catalytic reduction (SCR) is used. The SCR catalyst uses copper zeolite to achieve high levels of NOx conversion efficiency with minimal ammonia slip and unparalleled thermal durability. For particulate control, a diesel particulate filter (DPF) with upstream oxidation catalyst (DOC) is used. While the DPF may be actively regenerated when required, it operates predominantly with passive regeneration - enabled by the high NOx levels between the engine and the DPF, associated with high efficiency SCR systems and NO₂ production across the DOC.

Cu- and Fe-zeolite SCR catalysts emerged in recent years as the primary candidates for meeting the increasingly stringent lean exhaust emission regulations, due to their outstanding activity and durability characteristics. It is commonly known that Cu-zeolite catalysts possess superior activity to Fe-zeolites, in particular at low temperatures and sub-optimal NO₂/NOx ratios. In this work, we elucidate some underlying mechanistic differences between these two classes of catalysts, first based on their NO oxidation abilities, and then based on the relative properties of the two types of exchanged metal sites. Finally, by using the ammonia coverage-dependent NOx performance, we illustrate that state-of-the-art Fe-zeolites can perform better under certain transient conditions than in steady-state.

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.

Two hybrid powertrain configurations, including parallel and series hybrids, were simulated for fuel economy, component energy loss, and emissions control in Class 8 trucks over both city and highway driving conditions. A comprehensive set of component models describing engine fuel consumption, emissions control, battery energy, and accessory power demand interactions was developed and integrated with the simulated hybrid trucks to identify heavy-duty (HD) hybrid technology barriers. The results show that series hybrid is absolutely negative for fuel-economy improvement of long-haul trucks due to an efficiency penalty associated with the dual-step conversions of energy (i.e. mechanical to electric to mechanical).

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.

Future light duty vehicles in the United States are required to be certified on the FTP-75 cycle to meet Tier 3 or LEV III emission standards [1, 2]. The cold phase of this cycle is heavily weighted and mitigation of emissions during this phase is crucial to meet the low tail pipe emission targets [3, 4]. In this work, a novel aftertreatment architecture and controls to improve Nitrogen Oxides (NOx) and Hydrocarbon (HC) or Non Methane Organic gases (NMOG) conversion efficiencies at low temperatures is proposed. This includes a passive NOx & HC adsorber, termed the diesel Cold Start Concept (dCSC™) catalyst, followed by a Selective Catalytic Reduction catalyst on Filter (SCRF®) and an under-floor Selective Catalytic Reduction catalyst (SCR). The system utilizes a gaseous ammonia delivery system capable of dosing at two locations to maximize NOx conversion and minimize parasitic ammonia oxidation and ammonia slip.

Copper- and Iron- based metal-zeolite SCR catalysts are widely used in US and European diesel aftertreatment systems to achieve drastic reduction in NOx emission. These catalysts are highly selective to N2 under wide range of operating conditions. Nevertheless, the type of transition metal has a significant impact on the key performance and durability parameters such as NOx conversion, selectivity towards N2O, hydrothermal stability, and sensitivity to fuel sulfur content. In this study, we explained the differences in the performance characteristics of these catalysts based on their relative acidic-basic nature of transition metal present in these catalysts using practically relevant gas species present in diesel exhaust such as NO2, SOx, and NH3. These experiments show that Fe-zeolite has relatively acidic nature as compared to Cu-zeolite that causes NH3 inhibition and hence explains low NOx conversion on Fe-zeolite at low temperature under standard SCR conditions.

In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.

The influence of fuel rail pressure (FRP) and urea-selective catalytic reduction (SCR) on particulate matter (PM) formation is investigated in this paper along with notes regarding the NOx and other emissions. Increasing FRP was shown to reduce the overall soot and total PM mass for four operating conditions. These conditions included two high speed conditions (2400 rpm at 540 and 270 Nm of torque) and two moderated speed conditions (1400 rpm at 488 and 325 Nm). The concentrations of CO2 and NOx increased with fuel rail pressure and this is attributed to improved fuel-air mixing. Interestingly, the level of unburned hydrocarbons remained constant (or increased slightly) with increased FRP. PM concentration was measured using an AVL smoke meter and scanning mobility particle sizer (SMPS); and total PM was collected using standard gravimetric techniques. These results showed that the smoke number and particulate concentrations decrease with increasing FRP.

This study analyzed the impact of transient and multi-mode engine conditions on emissions of dioxins and furans from a variety of diesel aftertreatment configurations. Exhaust aftertreatment systems included combinations of diesel oxidation catalyst, diesel particulate filter, and either Cu/zeolite or Fe/zeolite selective catalytic reduction catalyst. EPA method TO-9A was modified for proportional exhaust gas sampling, whereas EPA method 0023A was modified for raw exhaust gas sampling. Dioxin and furan emissions were first measured with modified method TO-9A during Federal Test Procedure transient cycles, but no toxic dioxins or furans were detected. Measurements were then taken with modified method 0023A during Ramped Mode Cycles-Supplemental Emissions Test experiments. Because more rigorous pre-cleaning and sample extraction procedures were used with this method and lower detection limits were achieved by the analytical laboratory, some dioxin and furan congeners were detected.

The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst 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. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which has smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

The high global warming potential of nitrous oxide (N₂O) led to its recent inclusion in the list of regulated pollutants under the emerging greenhouse gas regulations. While N₂O can be present in small quantities among the combustion products, it can also be generated as a minor byproduct in various types of aftertreatment systems. In this work, a systematic review of sources of N₂O is presented, along with the potential mechanisms of formation in a typical selective-catalytic-reduction-based diesel exhaust aftertreatment system. It is demonstrated that diesel oxidation catalysts (DOC), selective catalytic reduction (SCR) catalyst, and ammonia slip catalyst (ASC) can all potentially contribute to N₂O formation, depending on the catalyst material and exhaust gas conditions, as well as aftertreatment operation strategies. Furthermore, catalysts used in SCR aftertreatment system are also shown to decompose and/or reduce N₂O to N₂ under select conditions.

Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.

Production NO sensors have a strong cross-sensitivity to ammonia which limits their use for closed-loop SCR control and diagnostics since increases in sensor output can be caused by either gas component. Recently, Ammonia/NO Ratio (ANR) perturbation methods have been proposed for determining the dominant component in the post-SCR exhaust as part of the overall SCR control strategy, but these methods or the issue of sensor cross-sensitivity have not been critically evaluated or studied in their own right. In this paper the dynamic sensor direct- and cross-sensitivities are estimated from experimental FTIR data (after compensating for the dynamics of the gas sampling system) and compared to nominal values provided by the manufacturer. The ANR perturbation method and the use of different input excitations are then discussed within an analytical framework, and applied to experimental data from a large diesel engine.

Cu/CHA catalysts have been widely used in the industry, due to their desirable performance characteristics including the unmatched hydrothermal stability. While broadly recognized for their outstanding activity at or above 200°C, these catalysts may not show desired levels of NOx conversion at lower temperatures. To achieve high NOx conversions it is desirable to have NO2/NOx close to 0.5 for fast SCR. However even under such optimal gas feed conditions, sustained use of Cu/CHA below 200°C leads to ammonium nitrate formation and accumulation, resulting in the inhibition of NOx conversion. In this contribution, the formation and decomposition of NH4NO3 on a commercial Cu/CHA catalyst have been investigated systematically. First, the impact of NH4NO3 self-inhibition on SCR activity as a function of temperature and NO2/NOx ratios was investigated through reactor testing.

For renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement.

In this contribution, nuanced changes of a commercial Cu-SSZ-13 catalyst with hydrothermal aging, which have not been previously reported, as well as their corresponding impact on SCR functions, are described. In particular, a sample of Cu-SSZ-13 was progressively aged between 550 to 900°C and the changes of performance in NH3 storage, oxidation functionality and NOx conversion of the catalyst were measured after hydrothermal exposure at each temperature. The catalysts thus aged were further characterized by NH3-TPD, XRD and DRIFTS techniques for structural changes. Based on the corresponding performance and structural characteristics, three different regimes of hydrothermal aging were identified, and tentatively as assigned to “mild”, “severe” and “extreme” aging. Progressive hydrothermal aging up to 750°C decreased NOx conversion to a small degree, as well as NH3 storage and oxidation functions.

Model-based control strategies are important for meeting the dual objective of maximizing NOx reduction and minimizing NH3 slip in urea-SCR catalysts. To be implementable on the vehicle, the models should capture the essential behavior of the system, while not being computationally intensive. This paper discusses the adequacy of two different reduced order SCR catalyst models and compares their performance with a higher order model. The higher order model assumes that the catalyst has both diffusion and reaction kinetics, whereas the reduced order models contain only reaction kinetics. After describing each model, its parameter identification and model validation based on experiments on a Navistar I6 7.6L engine are presented. The adequacy of reduced order models is demonstrated by comparing the NO, NO2 and NH3 concentrations predicted by the models to their concentrations from the test data.

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.