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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.

Porous wall permeability is one of the most critical factors for the estimation of backpressure, a key performance indicator in automotive particulate filters. Current experimental and analytical filter models could be calibrated to predict the permeability of a specific filter. However, they fail to provide a reliable estimation for the dependence of the permeability on key parameters such as wall porosity and pore size. This study presents a novel methodology for experimentally determining the permeability of filter walls. The results from four substrates with different porosities and pore sizes are compared with several popular permeability estimation methods (experimental and analytical), and their validity for this application is assessed. It is shown that none of the assessed methods predict all permeability trends for all substrates, for cold or hot flow, indicating that other wall properties besides porosity and pore size are important.

Diesel oxidation catalyst (DOC) is one of the critical catalyst components in modern diesel aftertreatment systems. It mainly converts unburned hydrocarbon (HC) and CO to CO2 and H2O before they are released to the environment. In addition, it also oxidizes a portion of NO to NO2, which improves the NOx conversion efficiency via fast SCR over the downstream selective catalytic reduction (SCR) catalyst. HC light-off tests, with or without the presence of NOx, has been typically used for DOC evaluation in laboratory. In this work, we aim to understand the influences of DOC light-off experimental conditions, such as initial temperature, initial holding time, HC species, with or without the presence of NOx, on the DOC HC light-off behavior. The results indicate that light-off test with lower initial temperature and longer initial holding time (at its initial temperature) leads to higher DOC light-off temperature.

With the advent of stricter vehicle emission standards, the improvement of three way catalyst performance and durability remains a pressing issue. A critical consideration in catalyst design is the potential for variations in fuel sulfur levels to have a significant impact on the ability to reach TLEV, LEV, and ULEV emission levels. As a result, a better understanding of the role of PGM composition in the interplay between thermal durability and sulfur tolerance is required. Three way catalysts representative of standard Pd-only, Pd/Rh and Pt/Rh formulations were studied over a variety of aging and evaluation conditions. The parameters investigated included aging temperature, air fuel ratio and sulfur level. Evaluations were performed on a 1994 TLEV vehicle using different sulfur level fuels. The effect of PGM loading was also included within the study.

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.

Sustained NOx reduction at low temperatures, especially in the 150-200 °C range, shares some similarities with the more commonly discussed cold-start challenge, however, poses a number of additional and distinct technical problems. In this project, we set a bold target of achieving and maintaining 90% NOx conversion at the SCR catalyst inlet temperature of 150 °C. This project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015 and completed in 2017.

The low-temperature performance characteristics of a commercial lean NOX trap catalyst were evaluated using infra-red thermography (IRT) before and after a high-temperature aging step. Reaction tests included propylene oxidation, oxygen storage capacity measurements, and simulated cycling conditions for NOX reduction, using H₂ as the reductant during the regeneration step of the cycle. Testing with and without NO in the lean phase showed thermal differences between the reductant used in reducing the stored oxygen and that for nitrate decomposition and reduction. IRT clearly demonstrated where NOX trapping and regeneration were occurring spatially as a function of regeneration conditions, with variables including hydrogen content of the regeneration phase and lean- and rich-phase cycle times.

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.

Heavy-duty diesel on-board diagnostics (OBD) regulations are being phased in around the world with varying degrees of similarity. This is occurring at a time when heavy-duty diesel emission regulations are driving complex and elaborate emission control strategies. Unique circumstances led the European heavy-duty diesel market to adopt selective catalytic reduction (SCR) as the primary solution for meeting strict Euro 4 emission levels. This paper is a review of the challenges of diagnosing an SCR system based on the Euro 4 OBD regulation and considers the future challenges of SCR diagnostics that lie ahead in the North American market.

In a consortium of European industrial partners and research institutes, a combination of industrial development and scientific research was organised. The objective was to improve the catalytic NOx conversion for lean burn cars and heavy-duty trucks, taking into account boundary conditions for the fuel consumption. The project lasted for three years. During this period parallel research was conducted in research areas ranging from basic research based on a theoretical approach to full scale emission system development. NOx storage catalysts became a central part of the project. Catalysts were evaluated with respect to resistance towards sulphur poisoning. It was concluded that very low sulphur fuel is a necessity for efficient use of NOx trap technology. Additionally, attempts were made to develop methods for reactivating poisoned catalysts. Methods for short distance mixing were developed for the addition of reducing agent.

In April 2003, a small field study was initiated to evaluate the effect of lube oil formulations on ash accumulation in heavy-duty diesel DPFs. Nine (9) Fuel Delivery Trucks were retrofitted with passive diesel particulate filters and fueled with ultra low sulfur diesel which contains less than 15 ppm sulfur. Each vehicle operated in the field for 18 months or approximately 160,000 miles (241,401 km) using one of three lube oil formulations. Ash accumulation was determined for each vehicle and compared between the three differing lube oil formulations. Ash analyses, used lube oil analysis and filter substrate evaluations were performed to provide a complete picture of DPF operations. The evaluation also examined some of the key parameters that allows for the successful implementation of the passive DPF in this heavy-duty application.

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.

In August of 2011, the US Environmental Protection Agency issued new Green House Gas (GHG) emissions regulations for heavy duty vehicles. These regulations included new procedures for the evaluation of hybrid powertrains and vehicles. One of the hybrid options allows for the evaluation of an engine plus a hybrid transmission (a powertrain). For this type of testing, EPA has proposed simulating a vehicle following the hybrid vehicle test procedures, including the use of the vehicle cycles and the A to B comparison testing - as required for the full vehicle evaluation option. This paper proposes an alternative approach by defining a powertrain cycle. The powertrain cycle is based on the heavy duty engine emissions cycle - the transient FTP cycle. Simulation and test results are presented showing similar performance over the engine and vehicle cycles. This approach offers several advantages as compared to the procedure described in EPA's GHG rule.

Accumulation of lubricant and fuel derived ash in the diesel particulate filter (DPF) during vehicle operation results in a significant increase of pressure drop across the after-treatment system leading to loss of fuel economy and reduced soot storage capacity over time. Under certain operating conditions, the accumulated ash and/or soot cake layer can collapse resulting in ash deposits upstream from the typical ash plug section, henceforth termed mid-channel ash deposits. In addition, ash particles can bond (either physically or chemically) with neighboring particles resulting in formation of bridges across the channels that effectively block access to the remainder of the channel for the incoming exhaust gas stream. This phenomenon creates serious long-term durability issues for the DPF, which often must be replaced. Mid-channel deposits and ash bridges are extremely difficult to remove from the channels as they often sinter to the substrate.

The objective of this effort was to develop an understanding of how different converter substrate cell structures impact tailpipe emissions and pressure drop from a total systems perspective. The cell structures studied were the following: The catalyst technologies utilized were a new technology palladium only catalyst in combination with a palladium/rhodium catalyst. A 4.0-liter, 1997 Jeep Cherokee with a modified calibration was chosen as the test platform for performing the FTP test. The experimental design focused on quantifying emissions performance as a function of converter volume for the different cell structures. The results from this study demonstrate that the 93 square cell/cm2 structure has superior performance versus the 62 square cell/cm2 structure and the 46 triangle cell/cm2 structure when the converter volumes were relatively small. However, as converter volume increases the emissions differences diminish.

The effect of changing catalyst precious metal ratios and loadings on close coupled catalytic converter efficiencies has been studied. The three precious metals were platinum, palladium and rhodium. The specific matrix used for the development of response surface models is a central composite design and provides the capability of visually optimising the precious metal loadings. Catalysts were evaluated using perturbed scans. lightoff curves from the dynamometer aged, and vehicle emission tests. These scans show percent conversion efficiencies of the three legislated gases; HC, CO and NOx, over a range of Air Fuel Ratios (λ). Whilst lean and rich lightoff curves provide indications of conversion efficiencies at varying temperatures. Prior to testing the catalysts were aged, using an accelerated dynamometer ageing process, to 80K simulated kilometres. The catalysts were then fitted to a vehicle and chassis roll emission tests conducted.

When performing catalyst modeling and parameter tuning it is desirable that the experimental data contain both transient and stationary points and can be generated over a short period of time. Here a method of creating such concentration transients for a full scale engine rig system is presented. The paper describes a valuable approach for changing the composition of engine exhaust gas going to a DOC (or potentially any other device) by conditioning the exhaust gas with an additional upstream DOC and/or SCR. By controlling the urea injection and the DOC bypass a wide range of exhaust compositions, not possible by only controlling the engine, could be achieved. This will improve the possibilities for parameter estimation for the modeling of the DOC.

An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.

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.

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.