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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.

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.

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 1-dimensional analytic solution has been developed to evaluate the pressure drop and filtration performance of ceramic wall-flow partial diesel particulate filters (PFs). An axially resolved mathematical model for the static pressure and velocity profiles prevailing inside wall-flow filters, with such unique plugging configurations, is being proposed for the first time. So far, the PF models that have been developed are either iterative/numerical in nature [1], or based on commercial CFD packages [7]. In comparison, an analytic solution approach is a transparent and computationally inexpensive tool that is capable of accurately predicting trends as well as, offering explanations to fundamental performance behavior. The simple mathematical expressions that have been obtained facilitate rational decision-making when designing partial filters, and could also reduce the complexity of OBD logic necessary to control onboard filter performance.

Exposure of hydrocarbons (HCs) and particulate matter (PM) under certain real-world operating conditions leads to carbonaceous deposit formation on V-SCR catalysts and causes reversible degradation of its NOx conversion. In addition, uncontrolled oxidation of such carbonaceous deposits can also cause the exotherm that can irreversibly degrade V-SCR catalyst performance. Therefore carbonaceous deposit mitigation strategies, based on their characterization, are needed to minimize their impact on performance. The nature and the amount of the deposits, formed upon exposure to real-world conditions, were primarily carried out by the controlled oxidation of the deposits to classify these carbonaceous deposits into three major classes of species: i) HCs, ii) coke, and iii) soot. The reversible NOx conversion degradation can be largely correlated to coke, a major constituent of the deposit, and to soot which causes face-plugging that leads to decreased catalyst accessibility.

Typical Lean NOx Trap (LNT) catalyst composition includes precious metal components (Pt, Pd, and/or Rh), responsible for NO oxidation during lean operation and NOx reduction during rich operation. It was found that redox history of commercial LNT catalyst plays a significant role on deciding its NOx conversion under Lean/Rich cyclic condition. Further test had shown that fully formulated LNT catalyst being pre-reduced had shown much better NO reduction activity during the temperature-programmed reduction (TPRx) of NO than the same LNT catalyst being oxidized. The following study with Rh-only and Pt-only catalyst had demonstrated that Rh plays a key role on the large variation of the NO reduction function due to oxidation state change over LNT 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.

Regeneration of diesel particulate filters poses major challenges in developing the particulate matter emission control technology to meet EPA 2007/2010 emissions regulations. The problem areas are multifold due to the complexity involved in designing the filter system, developing regeneration strategies and controlling the regeneration process. This paper discusses the need for active regeneration systems. It also addresses several key limitations and trade-offs between the regeneration strategy, chemical kinetics, exhaust gas temperature and the regeneration efficiency. Passive regeneration of diesel particulate filter systems is known to be highly dependent on the engine-out [NOx/PM] ratio as well as exhaust temperature over the duty cycle. Using catalytic oxidation of auxiliary fuel injected into the system, the exhaust gas temperature can be successfully enhanced for filter regeneration.

Real-world operation of diesel oxidation catalysts (DOCs), used in a variety of aftertreatment systems, subjects these catalysts to a large number of permanent and temporary deactivation mechanisms. These include thermal damage, induced by generating exotherm on the catalyst; exposure to various inorganic species contained in engine fluids; and the effects of soot and hydrocarbons, which can mask the catalyst in certain operating modes. While some of these deactivation mechanisms can be accurately simulated in the lab, others are specific to particular engine operation regimes. In this work, a set of DOCs, removed from prolonged service in the field, has been subjected to a detailed laboratory study. Samples obtained from various locations in these catalysts were used to characterize the extent and distribution of deactivation.

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.

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.

Results of computations of flows, sprays and combustion performed in an optically- accessible Diesel engine are presented. These computed results are compared with measured values of chamber pressure, liquid penetration, and soot distribution, deduced from flame luminosity photographs obtained in the engine at Sandia National Laboratories and reported in the literature. The computations were performed for two operating conditions representing low load and high load conditions as reported in the experimental work. The computed and measured peak pressures agree within 5% for both the low load and the high load conditions. The heat release rates derived from the computations are consistent with expectations for Diesel combustion with a premixed phase of heat release and then a diffusion phase. The computed soot distribution shows noticeable differences from the measured one.

Numerical computations of combusting transient jets are performed under diesel-like conditions. Discussions of the structure of such jets are presented from global and detailed points of view. From a global point of view, we show that the computed flame heights agree with deductions from theory and that integrated soot mass and heat release rates are consistent with expected trends. We present results of several paramaters which characterise the details of the jet structure. These are fuel mass fractions, temperature, heat release rates, soot and NO. Some of these parameters are compared with the structure of a combusting diesel spray as deduced from measurements and reported in the literature. The heat release rate contours show that the region of chemical reactions is confined to a thin sheet as expected for a diffusion flame. The soot contour plots appear to agree qualitatively with the experimental observations.

A fast time-scale 1-D dynamic diesel particulate filter model capable of resolving the pressure pulsations due to individual cylinder firing events is presented. The purpose of this model is to investigate changes in the firing frequency component of the pulsating exhaust flow at different particulate loadings. Experimental validation data and simulation results clearly show that the magnitude and phase of the firing frequency components are directly correlated to the mass of particulate stored in a diesel particulate filter. This dynamic pressure signal information may prove particularly useful for monitoring particulate load during vehicle operation.

The performance characteristics of a commercial lean-NOX trap catalyst were evaluated between 200 and 500°C, using H2, CO, and a mixture of both H2 and CO as reductants before and after different high-temperature aging steps, from 600 to 750°C. Tests included NOX reduction efficiency during cycling, NOX storage capacity (NSC), oxygen storage capacity (OSC), and water-gas-shift (WGS) and NO oxidation reaction extents. The WGS reaction extent at 200 and 300°C was negatively affected by thermal degradation, but at 400 and 500°C no significant change was observed. Changes in the extent of NO oxidation did not show a consistent trend as a function of thermal degradation. The total NSC was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation but a steady decrease was observed at 350°C as the thermal degradation temperature was increased.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure.

Multidimensional models are increasingly employed to predict NO and soot emissions from Diesel engines. In the traditional approach, the ensemble-averaged values of variables are employed in the expressions for NO and soot formation and oxidation. In the mixture fraction averaged approach, the values of state variables and species concentrations are obtained from the structure of laminar diffusion flames. The source terms for NO and soot are then obtained by averaging across the mixture fraction coordinate with a probability density function. The clipped-Gaussian probability density function and profiles obtained by employing the OPPDIF code (part of the CHEMKIN package) for the laminar flame structure are employed in this work. The Zeldovich mechanism for NO formation and the Moss et al. formation and Nagle-Strickland-Constable oxidation model for soot have been employed to study the qualitative trends of pollutants in transient combusting Diesel jets.

Changing diesel engine emission requirements for 2002 have led many diesel engine manufacturers to incorporate cooled Exhaust Gas Recirculation, EGR, as a means of reducing NOx. This has resulted in higher levels of soot being present in used oils. This paper builds on earlier work with fresh oils and describes a study of the effect of highly sooted oils on the low temperature pumpability in diesel engines. Four experimental diesel engine oils, of varying MRV TP-1 viscosities, were run in a Mack T-8 engine to obtain a soot level ranging between 6.1 and 6.6%. These sooted oils were then run in a Cummins M11 engine installed in a low temperature cell. Times to lubricate critical engine components were measured at temperatures ranging between -10 °C and -25 °C. A clear correlation was established between the MRV TP-1 viscosity of a sooted oil and the time needed to lubricate critical engine components at a given test temperature.